WO2023058543A1 - Vinylidene fluoride polymer solution - Google Patents

Vinylidene fluoride polymer solution Download PDF

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Publication number
WO2023058543A1
WO2023058543A1 PCT/JP2022/036378 JP2022036378W WO2023058543A1 WO 2023058543 A1 WO2023058543 A1 WO 2023058543A1 JP 2022036378 W JP2022036378 W JP 2022036378W WO 2023058543 A1 WO2023058543 A1 WO 2023058543A1
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vinylidene fluoride
fluoride polymer
solvent
less
polymer solution
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PCT/JP2022/036378
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French (fr)
Japanese (ja)
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望 小田川
善幸 長澤
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株式会社クレハ
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Priority to JP2023552835A priority Critical patent/JPWO2023058543A1/ja
Priority to KR1020247010512A priority patent/KR20240048563A/en
Priority to CN202280062124.5A priority patent/CN117980401A/en
Publication of WO2023058543A1 publication Critical patent/WO2023058543A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride

Definitions

  • the present invention relates to a vinylidene fluoride polymer solution.
  • Vinylidene fluoride polymers are used in a wide range of applications due to their excellent weather resistance and chemical resistance. However, vinylidene fluoride polymers are difficult to dissolve in common solvents. Therefore, N-methylpyrrolidone (NMP) and acetone are used as solvents when it is necessary to dissolve a vinylidene fluoride polymer, such as paints and coating agents.
  • NMP N-methylpyrrolidone
  • acetone are used as solvents when it is necessary to dissolve a vinylidene fluoride polymer, such as paints and coating agents.
  • acetone has a low flash point and boiling point and is difficult to handle.
  • NMP can easily dissolve the vinylidene fluoride polymer and has a high boiling point, but in recent years its toxicity has become a concern, and legal regulations have become stricter.
  • hexamethylphosphoramide and dimethylsulfoxide are also known as solvents capable of dissolving vinylidene fluoride polymers. However, since these solvents also have relatively high freezing points, they cannot be said to be easy to handle.
  • Patent Document 1 describes a paint composition in which an acrylic resin and a vinylidene fluoride polymer are dissolved in cyclohexanone or the like.
  • the vinylidene fluoride polymer described in Patent Document 1 does not have sufficient solubility in a solvent when it is tried to be dissolved in a solvent by itself, and it is very difficult to dissolve. It became clear that it would take time. In other words, it has been very difficult with conventional techniques to dissolve a vinylidene fluoride polymer in a solvent that is less harmful to the environment and is easy to handle.
  • An object of the present invention is to provide a vinylidene fluoride polymer solution in which a vinylidene fluoride polymer is dissolved in a solvent that is easy to handle and has a low environmental load.
  • the present invention is a vinylidene fluoride polymer solution containing a vinylidene fluoride polymer and a solvent, wherein the solvent has a molecular weight of 100 or more and at least one structure selected from ethers, ketones, and esters. and the vinylidene fluoride polymer provides a vinylidene fluoride polymer solution that satisfies the following (A) to (C).
  • (A) contains a structural unit derived from vinylidene fluoride and a structural unit derived from a fluorine-containing alkyl vinyl compound; (C) In the X-ray diffraction pattern obtained by X-ray diffraction measurement, the diffraction angle has at least one maximum in the range of 10 ° or more and 19.9 ° or less, and the diffraction angle is 22 .
  • the maximum diffraction intensity in the range of 5° or more and 30° or less is less than or equal to the maximum diffraction intensity in the diffraction angle range of 10° or more and 19.9° or less.
  • FIG. 1 is an X-ray diffraction pattern of the vinylidene fluoride polymers A to G prepared in Examples of the present application when X-ray diffraction measurement was performed.
  • Vinylidene fluoride polymer contained in the vinylidene fluoride polymer solution of the present invention contains a structural unit derived from vinylidene fluoride and a structural unit derived from a fluorine-containing alkyl vinyl compound (requirements (A)).
  • the vinylidene fluoride polymer may contain at least a vinylidene fluoride-derived structure and one or more fluorine-containing alkylvinyl compound-derived structures. It may be a primary copolymer, or a terpolymer of vinylidene fluoride, a fluorine-containing alkyl vinyl compound, and another compound. In addition, additives such as polymer modifiers may be added to these copolymers. However, the total amount of structural units derived from vinylidene fluoride and structural units derived from a fluorine-containing alkylvinyl compound is preferably 90% by mass or more, preferably 95% by mass or more, relative to all structural units of the vinylidene fluoride polymer.
  • the total amount of the vinylidene fluoride-derived structural unit and the fluorine-containing alkyl vinyl compound-derived structural unit is within the above range, the solubility of the vinylidene fluoride polymer in the solvent described below tends to increase.
  • the amount of the structural units derived from vinylidene fluoride in the vinylidene fluoride polymer is 40%. ⁇ 75% by mass is preferable, and 51 to 70% by mass is more preferable. 55 to 68% by mass is more preferable.
  • the amount of structural units derived from vinylidene fluoride in the vinylidene fluoride polymer is 40% by mass or more, physical properties derived from vinylidene fluoride are likely to be exhibited.
  • the amount of structural units derived from vinylidene fluoride in the vinylidene fluoride polymer is 75% by mass or less, the amount of the structure derived from the fluorine-containing alkyl vinyl compound is sufficiently increased, and the solubility in the solvent described below is increased. easy to rise.
  • the amount of vinylidene fluoride-derived structural units in the vinylidene fluoride polymer can be identified by, for example, 19 F-NMR analysis.
  • the amount of the structural unit derived from vinylidene fluoride and the structural unit derived from the fluorine-containing alkyl vinyl compound is 100% by mass
  • the amount of the structural unit derived from the fluorine-containing alkyl vinyl compound in the vinylidene fluoride polymer is 25 to 60% by mass is preferable, 30 to 49% by mass is more preferable, and 32 to 45% by mass is even more preferable.
  • the amount of the structural unit derived from the fluorine-containing alkyl compound in the vinylidene fluoride polymer is 25% by mass or more, the solubility in the below-described solvent is improved.
  • the amount of the structural unit derived from the fluorine-containing alkyl vinyl compound in the vinylidene fluoride polymer is 60% by mass or less, the amount of the structure derived from the vinylidene fluoride is sufficiently increased, and the physical properties derived from the vinylidene fluoride are improved. easier to manifest.
  • the amount of the structural unit derived from the fluorine-containing alkyl vinyl compound in the vinylidene fluoride polymer can be specified by, for example, 19 F-NMR analysis.
  • the fluorine-containing alkylvinyl compound may be a compound having a vinyl group and a fluorine-containing alkyl group, and the vinylidene fluoride polymer may contain only one structural unit derived from the fluorine-containing alkylvinyl compound, or two It may contain more than Examples derived from fluorine-containing alkyl vinyl compounds include vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, fluoroalkyl vinyl ether, and perfluoroalkyl vinyl ether represented by perfluoromethyl vinyl ether. is included.
  • tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene are preferred, and hexafluoropropylene is particularly preferred, from the viewpoint of easily satisfying requirements (B) and (C) described below.
  • the vinylidene fluoride polymer may have structural units derived from monomers (hereinafter also referred to as "other monomers") other than vinylidene fluoride and fluorine-containing alkyl vinyl compounds.
  • other monomers include unsaturated basic acids and unsaturated basic acid esters.
  • the unsaturated basic acid may be an unsaturated carboxylic acid or a derivative thereof, examples of which include linear or branched unsaturated alkylene groups in which one or more carboxyl groups have 1 to 6 carbon atoms. Included are compounds bound by More specific examples of unsaturated basic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like.
  • the unsaturated basic acid ester is an ester compound derived from the unsaturated basic acid, and specific examples thereof include methyl acrylate, methyl methacrylate, monomethyl maleate, monoethyl maleate, and maleic acid. acid dimethyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, and the like.
  • the vinylidene fluoride polymer has a peak top in the range of 60°C to less than 100°C in the DSC curve obtained by differential scanning calorimetry in accordance with ASTM D3418 (requirement (B)).
  • a DSC curve is a curve obtained by performing differential scanning calorimetry while changing the temperature in accordance with ASTM D3418.
  • the temperature range for the measurement can be usually 20°C to 230°C.
  • a group of measured values that are convex on the endothermic side with respect to the baseline are regarded as peaks.
  • the definition of baseline in differential scanning calorimetry is shown below. An average value of heat flux and an average value of temperature at a plurality of measurement points in the range of 40° C. or higher and 41° C. or lower are calculated. Similarly, the average value of the heat flux and the average value of the temperature at a plurality of measurement points within the range of 120° C. or higher and 121° C. or lower are calculated.
  • the vinylidene fluoride polymer when the vinylidene fluoride polymer has a peak top in the range of 60°C or higher and lower than 100°C in the DSC curve, the vinylidene fluoride polymer softens or melts at 60°C or higher and lower than 100°C. easier. In other words, the diffusion motion of the molecular chains of the vinylidene fluoride polymer becomes faster in this temperature range, which promotes swelling and deentangling in the solvent, and facilitates dissolution in the later-described solvent. It is more preferable that the vinylidene fluoride polymer has a peak top in the range of 60° C. or more and less than 90° C. in the DSC curve.
  • the amount of structural units derived from vinylidene fluoride in the vinylidene fluoride polymer is preferable to adjust the amount of the structural unit derived from the fluoroalkylvinyl compound within the range described above.
  • the vinylidene fluoride polymer has at least one maximum value in the range of a diffraction angle of 10° or more and 19.9° or less in an X-ray diffraction pattern obtained by X-ray diffraction measurement, and a diffraction angle of 22
  • the maximum diffraction intensity in the range of .5° or more and 30° or less is equal to or less than the maximum diffraction intensity in the diffraction angle range of 10° or more and 19.9° or less (requirement (C)).
  • the above X-ray diffraction measurement is performed based on JIS K0131:1996.
  • having at least one maximum value in the range of 10° or more and 19.9° or less of the diffraction angle means that the X-ray diffraction pattern has a peak and the diffraction angle is 10° or more and 19.9° or less. It means having the maximum value of the peak in the range of .
  • Whether or not the X-ray diffraction pattern has a peak is judged as follows. First, a baseline is identified, as shown below. Then, the diffraction intensity at a point on the baseline is compared with the diffraction intensity on the X-ray diffraction pattern at the same diffraction angle.
  • the X-ray diffraction pattern is determined to have a peak when the diffraction intensity on the X-ray diffraction pattern shows 5 or more consecutive points and 1.5 times or more of the corresponding diffraction intensity on the baseline.
  • the diffraction intensity on the X-ray diffraction pattern is continuously 5 points or more, and the maximum value in the measured value group at which the diffraction intensity on the baseline is 1.5 times or more is specified, and the maximum value is at the diffraction angle 10. It is judged whether it falls within the range of 19.9° or less.
  • the baseline in X-ray diffraction measurement is defined as follows. An average value of diffraction angles and an average value of diffraction intensities at a plurality of measurement points within a diffraction angle range of 10.0° or more and less than 10.1° are calculated. Similarly, the average value of the diffraction angles and the average value of the diffraction intensity at a plurality of measurement points within the range of diffraction angles of 30.0° or more and less than 30.1° are calculated. Then, a straight line connecting two points of diffraction angle/diffraction intensity thus calculated is taken as a baseline.
  • the average value of multiple measurement points for calculating the baseline from the viewpoint of measurement accuracy that is, the average value of the measurement points of 10.0 ° or more and less than 10.1 °, and 30.0 ° or more and less than 30.1 ° It is desirable to use an average value of 5 or more points for each of the measurement points in the range. Moreover, when the weight of the sample used for measurement is 0.1 g or more, it is easy to obtain a highly accurate measurement value.
  • the X-ray diffraction pattern of a vinylidene fluoride polymer represents the crystallization state of the vinylidene fluoride polymer. Also, the position of the maximum value of the diffraction intensity in the X-ray diffraction pattern differs depending on the type of crystal structure.
  • the vinylidene fluoride polymer D (homopolymer of vinylidene fluoride) in Examples described later has a large number of maxima in the diffraction angle region of 10° or more and 30° or less
  • the vinylidene fluoride polymer can be said to contain many crystal structures (see Fig. 1).
  • a large amount of energy is required to dissolve such a vinylidene fluoride homopolymer in a solvent.
  • the solubility in the solvent described later is low. It became clear.
  • the vinylidene fluoride polymer G in Examples described later does not have a maximum value in the X-ray diffraction pattern, the vinylidene fluoride polymer does not have a crystal structure and becomes rubbery ( See Figure 1). In such a vinylidene fluoride polymer, it is difficult for the solvent to enter therein, and the solubility of the vinylidene fluoride polymer in the solvent is low.
  • the diffraction angle has at least one maximum in the range of 10 ° or more and 19.9 ° or less, and the maximum diffraction intensity in the diffraction angle range of 22.5 ° or more and 30 ° or less is 10 °.
  • a vinylidene fluoride polymer whose diffraction intensity is equal to or less than the maximum diffraction intensity in the range of 19.9° or less has remarkably high solubility in the solvent described later.
  • Such a vinylidene fluoride polymer is considered to have a high solubility in solvents because it has few crystal structures with low solubility in the solvents described above and is moderately easily penetrated by the solvent.
  • the vinylidene fluoride polymer that satisfies the above requirement (C) has the amount of structural units derived from vinylidene fluoride in the vinylidene fluoride polymer and the amount of structural units derived from the fluorine-containing alkyl vinyl compound within the above ranges. can be easily obtained by adjusting the
  • the vinylidene fluoride polymer may be prepared and post-preparation treatment may be performed under conditions that do not destroy the crystal structure in which the maximum diffraction angle appears in the range of 10° or more and 19.9° or less. preferable.
  • an example of the treatment for destroying the crystal structure includes a treatment of dissolving the prepared vinylidene fluoride polymer in a solvent such as acetone.
  • the weight average molecular weight of the vinylidene fluoride polymer satisfying the above requirements (A) to (C) is preferably 10,000 to 2,500,000, more preferably 50,000 to 2,000,000, and even more preferably 100,000 to 1,500,000.
  • the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the vinylidene fluoride polymer satisfying the above requirements (A) to (C) is obtained by copolymerizing vinylidene fluoride, a fluorine-containing alkyl vinyl compound, and, if necessary, other compounds by a known method.
  • can be prepared by Examples of methods for copolymerizing these include suspension polymerization, emulsion polymerization, solution polymerization, and the like.
  • emulsion polymerization is preferable from the viewpoint that a vinylidene fluoride polymer that satisfies the requirements (B) and (C) described above can be easily obtained. Since the vinylidene fluoride polymer copolymerized by emulsion polymerization has a small primary particle size, it is easy to disperse and the stability after dispersion is improved.
  • the solvent contained in the vinylidene fluoride polymer solution may contain at least an affinity solvent having a molecular weight of 100 or more and having at least one structure selected from ethers, ketones, and esters. Other solvents may be partially contained within a range that does not impair the purpose and effect of the above.
  • the amount of the affinity solvent is preferably 80% by mass or more, more preferably 90% by mass or more, relative to the total amount of the solvent.
  • the molecular weight of the affinity solvent is 100 or more, the polarity of the solvent having ether, ketone, and ester polar groups is moderately lowered, so that the above-mentioned vinylidene fluoride polymer and Affinity increases.
  • the molecular weight of the affinity solvent is preferably 100 or more and 251 or less, more preferably 100 or more and 201 or less, and even more preferably 100 or more and 161 or less.
  • the affinity solvent may contain only one of ether, ketone, and ester, or may contain two or more. Moreover, the solvent may contain only 1 type of affinity solvent, and may contain 2 or more types.
  • the octanol/water partition coefficient LogP of the affinity solvent is preferably 0 or more, more preferably 0 or more and 4 or less, even more preferably 0 or more and 3 or less, and even more preferably 0.5 or more and 2.9 or less.
  • the octanol/water partition coefficient of the affinity solvent is 0 or more, the water content of the vinylidene fluoride polymer solution becomes low, and the stability of the vinylidene fluoride polymer solution tends to increase.
  • the octanol/water partition coefficient LogP is the concentration Co of the affinity solvent in the octanol phase and is the common logarithm (Log(Co/Cw)) of the ratio of the affinity of the solvent to the concentration Cw of the solvent.
  • affinity solvent examples include diisobutyl ketone (molecular weight: 142, LogP: 2.56), methyl isobutyl ketone (molecular weight: 100, LogP: 1.31), isophorone (molecular weight: 138, LogP: 1 .67) and other ketones; ethyl methyl carbonate (molecular weight: 104, Log P: 1.21), amyl acetate (molecular weight: 130, Log P: 2.18), ethyl butyrate (molecular weight: 116, Log P: 1.85), Esters such as butyl butyrate (molecular weight: 144, LogP: 2.8), isopropyl acetate (molecular weight: 102, LogP: 1.3), ethyl propionate (molecular weight: 102, LogP: 1.21); 2-butoxy acetate Solvents including esters and ethers such as ethyl (molecular weight: 160, LogP:
  • isophorone, diisobutyl ketone, methyl isobutyl ketone, amyl acetate, isopropyl acetate, ethyl butyrate, butyl butyrate, and ethyl propionate are preferable as the affinity solvent from the viewpoint of handleability.
  • the vinylidene fluoride polymer solution may contain components other than the vinylidene fluoride polymer and the solvent, depending on the application and within a range that does not impair the object and effect of the present invention.
  • other types of resins such as acrylic resins, fillers such as inorganic fillers, and various additives may be further included.
  • the concentration of the vinylidene fluoride polymer in the vinylidene fluoride polymer solution is not particularly limited, the concentration is preferably 30% by mass or less. When the concentration of the vinylidene fluoride polymer is within this range, it is difficult for the vinylidene fluoride polymer to remain undissolved, and the stability of the vinylidene fluoride polymer tends to increase. Furthermore, it becomes easy to use the vinylidene fluoride polymer solution for various purposes.
  • the haze value of the vinylidene fluoride polymer solution is preferably 18% or less, more preferably 15% or less, and even more preferably 10% or less.
  • the haze value of the vinylidene fluoride polymer solution is 18% or less, it can be said that the vinylidene fluoride polymer is sufficiently dissolved in the solvent. Further, when the haze value is 18% or less, the vinylidene fluoride polymer is less likely to precipitate or separate over time.
  • the haze value of the vinylidene fluoride polymer solution was measured using NDH2000 manufactured by Nippon Denshoku Industries based on ISO 14782.
  • the method for preparing the vinylidene fluoride polymer solution is not particularly limited, and it can be prepared by mixing the vinylidene fluoride polymer and a solvent by a known method and dissolving the vinylidene fluoride polymer.
  • the vinylidene fluoride polymer and the solvent are preferably mixed at a temperature of 40° C. or higher and 150° C. or lower, more preferably 60° C. or higher and 100° C. or lower.
  • the temperature is 60° C. or higher, the vinylidene fluoride polymer tends to soften or dissolve.
  • the temperature is 100° C. or lower, the solvent is less likely to volatilize excessively, and a vinylidene fluoride polymer solution having a desired composition can be easily obtained.
  • the mixing time is preferably 3 minutes or more and 3 hours or less from the viewpoint of production efficiency, and more preferably 5 minutes or more and 2 hours or less.
  • a vinylidene fluoride polymer that satisfies the above requirements (A) to (C) is combined with a solvent containing the above-mentioned affinity solvent. Therefore, when the vinylidene fluoride polymer is dissolved in the solvent, It does not take much time, and the stability of the resulting vinylidene fluoride polymer solution can be improved.
  • the use of the vinylidene fluoride polymer solution is not particularly limited, and it can be used for various uses such as paints, coating agents, and various binders for non-aqueous electrolyte secondary batteries and all-solid-state batteries.
  • Vinylidene fluoride polymers A to G were prepared by the following method.
  • the initial pressure at this time was 2.5 MPa, and 53.3 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa. After that, the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
  • VDF-HFP copolymer a latex of a copolymer of vinylidene fluoride and hexafluoropropylene
  • the resin concentration of the latex was 20.6% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 221 nm.
  • the average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees).
  • the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (fluoride A vinylidene polymer A) was obtained.
  • the mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 63:37.
  • the initial pressure at this time was 2.5 MPa, and 48 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa. After that, the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
  • VDF-HFP copolymer a copolymer of vinylidene fluoride and hexafluoropropylene
  • the resin concentration of the latex was 20.6% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 100 nm.
  • the average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees). Thereafter, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (fluoride A vinylidene polymer B) was obtained.
  • the mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 55:45.
  • the initial pressure was 2.5 MPa, and 63 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa.
  • the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
  • the resin concentration of the latex was 20.9% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 180 nm.
  • the average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees). Thereafter, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (fluoride A vinylidene polymer C) was obtained.
  • the mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 80:20.
  • the resin concentration of the latex was 20.9% by mass, and the average particle diameter of the VDF homopolymer in the latex was 150 nm.
  • the average particle size of the VDF homopolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees). After that, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain vinylidene fluoride homopolymer particles (vinylidene fluoride homopolymer D). got
  • the initial pressure was 4.01 MPa, and 65 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa.
  • the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
  • the resin concentration of the latex was 20.9% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 129 nm.
  • the average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees). Thereafter, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (fluoride A vinylidene polymer E) was obtained.
  • the mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 91:9.
  • the initial pressure was 2.5 MPa, and 60 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa.
  • the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
  • the resin concentration of the latex was 20.9% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 210 nm.
  • the average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees). After that, the latex was frozen with liquid nitrogen and vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene. .
  • the granulated copolymer particles were dissolved by adding 5 parts by mass of acetone to 1 part by mass of the granulated copolymer particles. 10 parts by mass of hexane was added to this acetone solution, and the mixture was stirred and separated by filtration to obtain a rubber-like precipitate. The rubber-like precipitate was dried in a vacuum dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (vinylidene fluoride polymer F). The mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 70:30.
  • the composition of the vinylidene fluoride polymer G was VDF:TFE:HFP (mass ratio) of 61:24:15.
  • DSC curve For each vinylidene fluoride polymer, differential scanning calorimetry was performed in the range from 20° C. to 230° in accordance with ASTM D3418 using a Mettler STARe DSC1 (apparatus) to create a DSC curve. The measurement was performed under a temperature elevation rate of 10° C./min and a nitrogen flow of 50 mL/min. A group of measured values convex to the endothermic side with respect to the baseline was regarded as a peak, and a measured value corresponding to the maximum value of a curve formed by the group of measured values was defined as the peak top. The baseline was specified as follows. For the three measurement points in the range of 40° C. or higher and 41° C.
  • a straight line connecting two points of the average value of each measurement point in the range of 40 ° C. or higher and 41 ° C. or lower calculated in this way and the average value of each measurement point in the range of 120 ° C. or higher and 121 ° C. or lower is defined as the baseline. bottom.
  • X-ray diffraction measurement As an apparatus, Philips X'Pert-PRO was used.
  • the optical system was a Bragg-Brentano concentrated optical system, a Cu tube was used to generate X-rays, the voltage value was 45 kV, and the current value was 40 mA.
  • the X-ray was monochromatic using a Ni filter, and a movable slit (irradiation area: 1 cm x 1 cm) was used.
  • Polyimide Kapton tape was used when sample fixation was required.
  • X-ray diffraction measurement of each vinylidene fluoride polymer was performed based on JISK0131:1996 under the apparatus conditions as described above.
  • FIG. 1 shows the X-ray diffraction pattern of each vinylidene fluoride polymer.
  • the diffraction angle range of 10 ° or more and 19.9 ° or less is determined by the diffraction angle It was confirmed whether the diffraction intensity was equal to or less than the maximum diffraction intensity in the range of 10° or more and 19.9° or less.
  • the average value of the diffraction angle and the average value of the diffraction intensity at a plurality of measurement points in the range of diffraction angles of 10.0° or more and less than 10.1° in the X-ray diffraction measurement were calculated.
  • the average value of the diffraction angles and the average value of the diffraction intensity at a plurality of measurement points within the range of diffraction angles of 30.0° or more and less than 30.1° were calculated.
  • a straight line connecting two points of diffraction angle and diffraction intensity thus calculated was used as a baseline.
  • the diffraction intensity at the points on the baseline is compared with the diffraction intensity on the X-ray diffraction pattern at the same diffraction angle.
  • the X-ray diffraction pattern was judged to have a peak when the value was 1.5 times or more the diffraction intensity of .
  • the maximum value in the measured value group at which the diffraction intensity on the X-ray diffraction pattern is continuously 5 points or more and the diffraction intensity on the baseline is 1.5 times or more is specified, and the maximum value is at a diffraction angle of 10. It was specified whether it falls within the range of 19.9° or less.
  • the X-ray diffraction patterns of the vinylidene fluoride polymers F and G are in the range of diffraction angles of 10 ° or more and 19.9 ° or less, and the diffraction intensity of the measured value is 1 of the baseline diffraction intensity corresponding to It was judged that there was no maximum value because there was no point where the value was 0.5 times or more. Table 1 shows the results.
  • the present invention it is possible to obtain a vinylidene fluoride polymer solution in which the vinylidene fluoride polymer is completely dissolved in a solvent that has a low environmental load and is easy to handle.
  • the vinylidene fluoride polymer solution can be used in various fields.

Abstract

The present invention addresses the problem of providing a vinylidene fluoride polymer solution obtained by dissolving a vinylidene fluoride polymer in a solvent that imposes a small burden on the environment and that can be easily handled. A vinylidene fluoride polymer solution that solves said problem contains a vinylidene fluoride polymer and a solvent. The solvent has a molecular weight of 100 or more and includes an affinitive solvent having at least one structure selected from ether, ketone, and ester. The vinylidene fluoride polymer satisfies a specific requirement.

Description

フッ化ビニリデン重合体溶液Vinylidene fluoride polymer solution
　本発明は、フッ化ビニリデン重合体溶液に関する。 The present invention relates to a vinylidene fluoride polymer solution.
　フッ化ビニリデン重合体は、その耐候性、耐薬品性が優れること等から、幅広い用途に使用されている。ただし、フッ化ビニリデン重合体は、一般的な溶剤に溶解し難い。そのため、塗料やコーティング剤等、フッ化ビニリデン重合体を溶解させる必要がある場合には、溶媒としてＮ－メチルピロリドン（ＮＭＰ）やアセトンが使用されている。 Vinylidene fluoride polymers are used in a wide range of applications due to their excellent weather resistance and chemical resistance. However, vinylidene fluoride polymers are difficult to dissolve in common solvents. Therefore, N-methylpyrrolidone (NMP) and acetone are used as solvents when it is necessary to dissolve a vinylidene fluoride polymer, such as paints and coating agents.
　しかしながら、アセトンは引火点や沸点が低く、取り扱いが難しい。一方、ＮＭＰはフッ化ビニリデン重合体を容易に溶解させることが可能であり、かつ高沸点であるが、近年その毒性が懸念され、法的な規制が厳しくなっている。一方、フッ化ビニリデン重合体を溶解させることが可能な溶媒として、ヘキサメチルホスホルアミド、ジメチルスルホキシドも知られている。しかしながら、これらの溶媒も比較的凝固点が高いこと等から、取り扱いが容易とはいえない。 However, acetone has a low flash point and boiling point and is difficult to handle. On the other hand, NMP can easily dissolve the vinylidene fluoride polymer and has a high boiling point, but in recent years its toxicity has become a concern, and legal regulations have become stricter. On the other hand, hexamethylphosphoramide and dimethylsulfoxide are also known as solvents capable of dissolving vinylidene fluoride polymers. However, since these solvents also have relatively high freezing points, they cannot be said to be easy to handle.
　ここで、特許文献１には、アクリル樹脂およびフッ化ビニリデン重合体を、シクロヘキサノン等に溶解させた塗料用組成物が記載されている。 Here, Patent Document 1 describes a paint composition in which an acrylic resin and a vinylidene fluoride polymer are dissolved in cyclohexanone or the like.
特開平３－２２０２７２号公報JP-A-3-220272
　しかしながら、本発明者らが鋭意検討したところ、上記特許文献１に記載のフッ化ビニリデン重合体は、単独で溶媒に溶解させようとすると、溶媒への溶解性が十分でなく、溶解に非常に時間がかかることが明らかとなった。つまり、従来の技術では、環境への負荷が少なく、かつ取り扱い性が良好な溶媒に、フッ化ビニリデン重合体を溶解させることは非常に難しかった。 However, as a result of intensive studies by the present inventors, the vinylidene fluoride polymer described in Patent Document 1 does not have sufficient solubility in a solvent when it is tried to be dissolved in a solvent by itself, and it is very difficult to dissolve. It became clear that it would take time. In other words, it has been very difficult with conventional techniques to dissolve a vinylidene fluoride polymer in a solvent that is less harmful to the environment and is easy to handle.
　本発明は、上記課題を鑑みてなされたものである。環境への負荷が少なく、かつ取り扱いが容易な溶媒に、フッ化ビニリデン重合体が溶解したフッ化ビニリデン重合体溶液の提供を目的とする。 The present invention has been made in view of the above problems. An object of the present invention is to provide a vinylidene fluoride polymer solution in which a vinylidene fluoride polymer is dissolved in a solvent that is easy to handle and has a low environmental load.
　本発明は、フッ化ビニリデン重合体と、溶媒とを含むフッ化ビニリデン重合体溶液であり、前記溶媒は分子量１００以上であり、かつエーテル、ケトン、およびエステルから選択される少なくとも１種の構造を有する親和性溶媒を含み、前記フッ化ビニリデン重合体は、以下の（Ａ）～（Ｃ）を満たす、フッ化ビニリデン重合体溶液を提供する。
　（Ａ）フッ化ビニリデン由来の構成単位と、含フッ素アルキルビニル化合物由来の構成単位と、を含有する
　（Ｂ）ＡＳＴＭ　Ｄ３４１８に準拠した示差走査熱量測定により得られるＤＳＣ曲線の６０℃以上１００℃未満の範囲に、ピークトップを有する
　（Ｃ）Ｘ線回折測定により得られるＸ線回折パターンにおいて、回折角度が１０°以上１９．９°以下の範囲に少なくとも１つの極大値を有し、回折角度２２．５°以上３０°以下の範囲における最大回折強度が、回折角度１０°以上１９．９°以下の範囲における最大回折強度以下である The present invention is a vinylidene fluoride polymer solution containing a vinylidene fluoride polymer and a solvent, wherein the solvent has a molecular weight of 100 or more and at least one structure selected from ethers, ketones, and esters. and the vinylidene fluoride polymer provides a vinylidene fluoride polymer solution that satisfies the following (A) to (C).
(A) contains a structural unit derived from vinylidene fluoride and a structural unit derived from a fluorine-containing alkyl vinyl compound; (C) In the X-ray diffraction pattern obtained by X-ray diffraction measurement, the diffraction angle has at least one maximum in the range of 10 ° or more and 19.9 ° or less, and the diffraction angle is 22 .The maximum diffraction intensity in the range of 5° or more and 30° or less is less than or equal to the maximum diffraction intensity in the diffraction angle range of 10° or more and 19.9° or less.
　本発明によれば、環境への負荷が少なく、かつ取り扱いが容易な溶媒に、フッ化ビニリデン重合体が溶解したフッ化ビニリデン重合体溶液が得られる。 According to the present invention, it is possible to obtain a vinylidene fluoride polymer solution in which a vinylidene fluoride polymer is dissolved in a solvent that is easy to handle and has a low environmental load.
図１は、本願の実施例で調製したフッ化ビニリデン重合体Ａ～Ｇについて、Ｘ線回折測定を行ったときのＸ線回折パターンである。FIG. 1 is an X-ray diffraction pattern of the vinylidene fluoride polymers A to G prepared in Examples of the present application when X-ray diffraction measurement was performed.
　前述のように、一般的なフッ化ビニリデン重合体は、例えばエーテルやケトン、エステル等のような、環境への負荷が少なく、比較的取り扱いが容易な溶媒に溶解させることが難しかった。これに対し、本発明のフッ化ビニリデン重合体溶液では、後述の要件（Ａ）～（Ｃ）を満たすフッ化ビニリデン重合体と、分子量が１００以上であり、かつエーテル、ケトン、およびエステルから選択される少なくとも１種の構造を有する親和性溶媒を含む溶媒とを組み合わせる。これにより、フッ化ビニリデン重合体を上記溶媒に容易に溶解させることが可能となり、かつその安定性も良好になる。以下、当該フッ化ビニリデン重合体溶液における各成分について説明する。 As mentioned above, it is difficult to dissolve common vinylidene fluoride polymers in solvents such as ethers, ketones, esters, etc., which have a low environmental impact and are relatively easy to handle. On the other hand, in the vinylidene fluoride polymer solution of the present invention, a vinylidene fluoride polymer that satisfies the requirements (A) to (C) described later and a molecular weight of 100 or more and selected from ethers, ketones, and esters is combined with a solvent comprising an affinity solvent having at least one structure that is As a result, the vinylidene fluoride polymer can be easily dissolved in the solvent, and its stability is improved. Each component in the vinylidene fluoride polymer solution will be described below.
　・フッ化ビニリデン重合体
　本発明のフッ化ビニリデン重合体溶液が含むフッ化ビニリデン重合体は、フッ化ビニリデンに由来する構成単位と、含フッ素アルキルビニル化合物由来の構成単位と、を含有する（要件（Ａ））。 · Vinylidene fluoride polymer The vinylidene fluoride polymer contained in the vinylidene fluoride polymer solution of the present invention contains a structural unit derived from vinylidene fluoride and a structural unit derived from a fluorine-containing alkyl vinyl compound (requirements (A)).
　フッ化ビニリデン重合体は、少なくともフッ化ビニリデン由来の構造と、一種または二種以上の含フッ素アルキルビニル化合物由来の構造とを含んでいればよく、フッ化ビニリデンと含フッ素アルキルビニル化合物との二元系共重合体であってもよく、フッ化ビニリデンと含フッ素アルキルビニル化合物と、さらに他の化合物との三元系共重合体であってもよい。また、これらの共重合体にポリマー改質剤等の添加物を加えたものでもよい。ただし、フッ化ビニリデン重合体の全構造単位に対して、フッ化ビニリデン由来の構造単位と含フッ素アルキルビニル化合物由来の構造単位とを合計で、９０質量％以上含むことが好ましく、９５質量％以上含むことがより好ましく、９７質量％以上含むことがさらに好ましい。フッ化ビニリデン由来の構造単位と、含フッ素アルキルビニル化合物由来の構造単位との合計量が当該範囲であると、フッ化ビニリデン重合体の後述の溶媒に対する溶解性が高まりやすい。 The vinylidene fluoride polymer may contain at least a vinylidene fluoride-derived structure and one or more fluorine-containing alkylvinyl compound-derived structures. It may be a primary copolymer, or a terpolymer of vinylidene fluoride, a fluorine-containing alkyl vinyl compound, and another compound. In addition, additives such as polymer modifiers may be added to these copolymers. However, the total amount of structural units derived from vinylidene fluoride and structural units derived from a fluorine-containing alkylvinyl compound is preferably 90% by mass or more, preferably 95% by mass or more, relative to all structural units of the vinylidene fluoride polymer. More preferably, it contains 97% by mass or more. When the total amount of the vinylidene fluoride-derived structural unit and the fluorine-containing alkyl vinyl compound-derived structural unit is within the above range, the solubility of the vinylidene fluoride polymer in the solvent described below tends to increase.
　ここで、フッ化ビニリデン由来の構造単位と含フッ素アルキルビニル化合物由来の構造単位との合計を１００質量％とした場合、フッ化ビニリデン重合体中のフッ化ビニリデン由来の構造単位の量は、４０～７５質量％が好ましく、５１～７０質量％がより好ましい。５５～６８質量％がさらに好ましい。フッ化ビニリデン重合体中のフッ化ビニリデン由来の構造単位の量が４０質量％以上であると、フッ化ビニリデン由来の物性が発現しやすくなる。一方、フッ化ビニリデン重合体中のフッ化ビニリデン由来の構造単位の量が７５質量％以下であると、含フッ素アルキルビニル化合物由来の構造の量が十分に多くなり、後述の溶媒に対する溶解性が高まりやすい。なお、フッ化ビニリデン重合体中のフッ化ビニリデン由来の構造単位の量は、例えば１９Ｆ－ＮＭＲによる分析等によって特定可能である。 Here, when the total of the structural units derived from vinylidene fluoride and the structural units derived from the fluorine-containing alkyl vinyl compound is 100% by mass, the amount of the structural units derived from vinylidene fluoride in the vinylidene fluoride polymer is 40%. ~75% by mass is preferable, and 51 to 70% by mass is more preferable. 55 to 68% by mass is more preferable. When the amount of structural units derived from vinylidene fluoride in the vinylidene fluoride polymer is 40% by mass or more, physical properties derived from vinylidene fluoride are likely to be exhibited. On the other hand, when the amount of structural units derived from vinylidene fluoride in the vinylidene fluoride polymer is 75% by mass or less, the amount of the structure derived from the fluorine-containing alkyl vinyl compound is sufficiently increased, and the solubility in the solvent described below is increased. easy to rise. The amount of vinylidene fluoride-derived structural units in the vinylidene fluoride polymer can be identified by, for example, 19 F-NMR analysis.
　一方、フッ化ビニリデン由来の構造単位と含フッ素アルキルビニル化合物由来の構造単位との合計を１００質量％とした場合、フッ化ビニリデン重合体中の含フッ素アルキルビニル化合物由来の構造単位の量は、２５～６０質量％が好ましく、３０～４９質量％がより好ましく、３２～４５質量％がさらに好ましい。フッ化ビニリデン重合体中の含フッ素アルキル化合物由来の構造単位の量が２５質量％以上であると、後述の溶媒に対する溶解性が良好になる。一方、フッ化ビニリデン重合体中の含フッ素アルキルビニル化合物由来の構造単位の量が６０質量％以下であると、フッ化ビニリデン由来の構造の量が十分に多くなり、フッ化ビニリデン由来の物性が発現しやすくなる。フッ化ビニリデン重合体中の含フッ素アルキルビニル化合物由来の構造単位の量は、例えば１９Ｆ－ＮＭＲによる分析等によって特定可能である。 On the other hand, when the total amount of the structural unit derived from vinylidene fluoride and the structural unit derived from the fluorine-containing alkyl vinyl compound is 100% by mass, the amount of the structural unit derived from the fluorine-containing alkyl vinyl compound in the vinylidene fluoride polymer is 25 to 60% by mass is preferable, 30 to 49% by mass is more preferable, and 32 to 45% by mass is even more preferable. When the amount of the structural unit derived from the fluorine-containing alkyl compound in the vinylidene fluoride polymer is 25% by mass or more, the solubility in the below-described solvent is improved. On the other hand, when the amount of the structural unit derived from the fluorine-containing alkyl vinyl compound in the vinylidene fluoride polymer is 60% by mass or less, the amount of the structure derived from the vinylidene fluoride is sufficiently increased, and the physical properties derived from the vinylidene fluoride are improved. easier to manifest. The amount of the structural unit derived from the fluorine-containing alkyl vinyl compound in the vinylidene fluoride polymer can be specified by, for example, 19 F-NMR analysis.
　上記含フッ素アルキルビニル化合物は、ビニル基および含フッ素アルキル基を有する化合物であればよく、フッ化ビニリデン重合体は、含フッ素アルキルビニル化合物由来の構成単位を一種のみ含んでいてもよく、二種以上含んでいてもよい。含フッ素アルキルビニル化合物由来の例には、フッ化ビニル、トリフルオロエチレン、テトラフルオロエチレン、クロロトリフルオロエチレン、ヘキサフルオロプロピレン、フルオロアルキルビニルエーテル、およびパーフルオロメチルビニルエーテルに代表されるパーフルオロアルキルビニルエーテル等が含まれる。これらのうち、後述の要件（Ｂ）や要件（Ｃ）を満たしやすくなる観点で、テトラフルオロエチレン、クロロトリフルオロエチレンおよびヘキサフルオロプロピレンが好ましく、ヘキサフルオロプロピレンが特に好ましい。 The fluorine-containing alkylvinyl compound may be a compound having a vinyl group and a fluorine-containing alkyl group, and the vinylidene fluoride polymer may contain only one structural unit derived from the fluorine-containing alkylvinyl compound, or two It may contain more than Examples derived from fluorine-containing alkyl vinyl compounds include vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, fluoroalkyl vinyl ether, and perfluoroalkyl vinyl ether represented by perfluoromethyl vinyl ether. is included. Among these, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene are preferred, and hexafluoropropylene is particularly preferred, from the viewpoint of easily satisfying requirements (B) and (C) described below.
　また、上述のように、フッ化ビニリデン重合体は、フッ化ビニリデンおよび含フッ素アルキルビニル化合物以外のモノマー（以下、「その他のモノマー」とも称する）由来の構造単位を有していてもよい。その他のモノマーの例には、不飽和塩基酸および不飽和塩基酸エステル等が含まれる。 Further, as described above, the vinylidene fluoride polymer may have structural units derived from monomers (hereinafter also referred to as "other monomers") other than vinylidene fluoride and fluorine-containing alkyl vinyl compounds. Examples of other monomers include unsaturated basic acids and unsaturated basic acid esters.
　不飽和塩基酸は、不飽和カルボン酸またはその誘導体であればよく、その例には、１つ以上のカルボキシル基が、炭素数１以上６以下の直鎖状または分岐鎖状の不飽和アルキレン基によって結合された化合物が含まれる。不飽和塩基酸のより具体的な例には、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、およびシトラコン酸等が含まれる。 The unsaturated basic acid may be an unsaturated carboxylic acid or a derivative thereof, examples of which include linear or branched unsaturated alkylene groups in which one or more carboxyl groups have 1 to 6 carbon atoms. Included are compounds bound by More specific examples of unsaturated basic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like.
　また、不飽和塩基酸エステルは、上記不飽和塩基酸に由来するエステル化合物であり、その具体例には、アクリル酸メチルエステル、メタクリル酸メチルエステル、マレイン酸モノメチルエステル、マレイン酸モノエチルエステル、マレイン酸ジメチルエステル、シトラコン酸モノメチルエステル、およびシトラコン酸モノエチルエステル等が含まれる。 The unsaturated basic acid ester is an ester compound derived from the unsaturated basic acid, and specific examples thereof include methyl acrylate, methyl methacrylate, monomethyl maleate, monoethyl maleate, and maleic acid. acid dimethyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, and the like.
　ここで、上記フッ化ビニリデン重合体は、ＡＳＴＭ　Ｄ３４１８に準拠した示差走査熱量測定により得られるＤＳＣ曲線の６０℃以上１００℃未満の範囲に、ピークトップを有する（要件（Ｂ））。 Here, the vinylidene fluoride polymer has a peak top in the range of 60°C to less than 100°C in the DSC curve obtained by differential scanning calorimetry in accordance with ASTM D3418 (requirement (B)).
　ＤＳＣ曲線は、ＡＳＴＭ　Ｄ３４１８に準拠して温度を変化させながら示差走査熱量測定を行って、得られる曲線である。測定の際の温度範囲は、通常２０℃～２３０℃とすることができる。また、本明細書では、ベースラインに対して吸熱側に凸である測定値群をピークとみなす。なお、示差走査熱量測定におけるベースラインの定義を以下に示す。４０℃以上４１℃以下の範囲にある複数の測定点の熱流束の平均値および温度の平均値をそれぞれ算出する。同様に１２０℃以上１２１℃以下の範囲にある複数の測定点の熱流束の平均値および温度の平均値をそれぞれ算出する。このように算出された４０℃以上４１℃以下の範囲にある、複数の測定点の平均値と、１２０℃以上１２１℃以下の範囲にある、複数の測定点の平均値との２点を結ぶ直線をベースラインとする。なお、示差走査熱量測定では、各温度範囲（４０℃以上４１℃以下、および１２０℃以上１２１℃以下）にある測定点が３点以上となるように測定することが望ましい。 A DSC curve is a curve obtained by performing differential scanning calorimetry while changing the temperature in accordance with ASTM D3418. The temperature range for the measurement can be usually 20°C to 230°C. Also, in this specification, a group of measured values that are convex on the endothermic side with respect to the baseline are regarded as peaks. The definition of baseline in differential scanning calorimetry is shown below. An average value of heat flux and an average value of temperature at a plurality of measurement points in the range of 40° C. or higher and 41° C. or lower are calculated. Similarly, the average value of the heat flux and the average value of the temperature at a plurality of measurement points within the range of 120° C. or higher and 121° C. or lower are calculated. Connect two points, the average value of a plurality of measurement points in the range of 40° C. or higher and 41° C. or lower calculated in this way, and the average value of a plurality of measurement points in the range of 120° C. or higher and 121° C. or lower. Use a straight line as the baseline. In the differential scanning calorimetry, it is desirable to measure at three or more points in each temperature range (40° C. or higher and 41° C. or lower and 120° C. or higher and 121° C. or lower).
　ここで、フッ化ビニリデン重合体が、上記ＤＳＣ曲線の６０℃以上１００℃未満の範囲にピークトップを有すると、フッ化ビニリデン重合体が６０℃以上１００℃未満で軟化したり、溶融したりしやすくなる。つまり、当該温度範囲でフッ化ビニリデン重合体の分子鎖の拡散運動が速くなることから、溶媒への膨潤および脱絡み合いが促進され、後述の溶媒に容易に溶解しやすくなる。なお、フッ化ビニリデン重合体は、上記ＤＳＣ曲線において、６０℃以上９０℃未満の範囲にピークトップを有することが、より好ましい。 Here, when the vinylidene fluoride polymer has a peak top in the range of 60°C or higher and lower than 100°C in the DSC curve, the vinylidene fluoride polymer softens or melts at 60°C or higher and lower than 100°C. easier. In other words, the diffusion motion of the molecular chains of the vinylidene fluoride polymer becomes faster in this temperature range, which promotes swelling and deentangling in the solvent, and facilitates dissolution in the later-described solvent. It is more preferable that the vinylidene fluoride polymer has a peak top in the range of 60° C. or more and less than 90° C. in the DSC curve.
　フッ化ビニリデン重合体を、ＤＳＣ曲線が６０℃以上１００℃未満の範囲にピークトップを有するように調整するためには、フッ化ビニリデン重合体中のフッ化ビニリデン由来の構造単位の量、および含フッ素アルキルビニル化合物由来の構造単位の量を上述の範囲に調整することが好ましい。 In order to adjust the vinylidene fluoride polymer so that the DSC curve has a peak top in the range of 60° C. or more and less than 100° C., the amount of structural units derived from vinylidene fluoride in the vinylidene fluoride polymer and It is preferable to adjust the amount of the structural unit derived from the fluoroalkylvinyl compound within the range described above.
　また、上記フッ化ビニリデン重合体は、Ｘ線回折測定により得られるＸ線回折パターンにおいて、回折角度が１０°以上１９．９°以下の範囲に少なくとも１つの極大値を有し、かつ回折角度２２．５°以上３０°以下の範囲における最大回折強度が、回折角度１０°以上１９．９°以下の範囲における最大回折強度以下である（要件（Ｃ））。 In addition, the vinylidene fluoride polymer has at least one maximum value in the range of a diffraction angle of 10° or more and 19.9° or less in an X-ray diffraction pattern obtained by X-ray diffraction measurement, and a diffraction angle of 22 The maximum diffraction intensity in the range of .5° or more and 30° or less is equal to or less than the maximum diffraction intensity in the diffraction angle range of 10° or more and 19.9° or less (requirement (C)).
　ここで、上記Ｘ線回折測定は、ＪＩＳ　Ｋ０１３１：１９９６に基づいて行う。本明細書において、回折角度が１０°以上１９．９°以下の範囲に少なくとも１つの極大値を有するとは、Ｘ線回折パターンがピークを有し、かつ回折角度１０°以上１９．９°以下の範囲に、当該ピークの極大値を有することをいう。Ｘ線回折パターンがピークを有するかは、以下のように判断する。まず、下記に示すように、ベースラインを特定する。そして、当該ベースライン上の点の回折強度と、同一の回折角度におけるＸ線回折パターン上の回折強度とを比較する。Ｘ線回折パターン上の回折強度が連続して５点以上、対応するベースライン上の回折強度の１．５倍以上の値を示す場合に、当該Ｘ線回折パターンがピークを有すると判断する。また、Ｘ線回折パターン上の回折強度が連続して５点以上、ベースライン上の回折強度の１．５倍以上となる測定値群における極大値を特定し、当該極大値が、回折角度１０°以上１９．９°以下の範囲に入るかを判断する。 Here, the above X-ray diffraction measurement is performed based on JIS K0131:1996. In this specification, having at least one maximum value in the range of 10° or more and 19.9° or less of the diffraction angle means that the X-ray diffraction pattern has a peak and the diffraction angle is 10° or more and 19.9° or less. It means having the maximum value of the peak in the range of . Whether or not the X-ray diffraction pattern has a peak is judged as follows. First, a baseline is identified, as shown below. Then, the diffraction intensity at a point on the baseline is compared with the diffraction intensity on the X-ray diffraction pattern at the same diffraction angle. The X-ray diffraction pattern is determined to have a peak when the diffraction intensity on the X-ray diffraction pattern shows 5 or more consecutive points and 1.5 times or more of the corresponding diffraction intensity on the baseline. In addition, the diffraction intensity on the X-ray diffraction pattern is continuously 5 points or more, and the maximum value in the measured value group at which the diffraction intensity on the baseline is 1.5 times or more is specified, and the maximum value is at the diffraction angle 10. It is judged whether it falls within the range of 19.9° or less.
　本明細書では、Ｘ線回折測定におけるベースラインを、以下のように定義する。回折角度１０．０°以上１０．１°未満の範囲にある複数の測定点の回折角度の平均値および回折強度の平均値をそれぞれ算出する。同様に回折角度３０．０°以上３０．１°未満の範囲にある複数の測定点の回折角度の平均値および回折強度の平均値をそれぞれ算出する。そして、このように算出された回折角度・回折強度の値２点を結ぶ直線をベースラインとする。測定精度の観点からベースラインを算出するための複数の測定点の平均値、すなわち１０．０°以上１０．１°未満の測定点の平均値、および３０．０°以上３０．１°未満の範囲の測定点の平均値は、それぞれ５点以上の平均値を用いることが望ましい。また、測定に用いるサンプル重量が０．１ｇ以上であると、精度の良い測定値が得られやすい。 In this specification, the baseline in X-ray diffraction measurement is defined as follows. An average value of diffraction angles and an average value of diffraction intensities at a plurality of measurement points within a diffraction angle range of 10.0° or more and less than 10.1° are calculated. Similarly, the average value of the diffraction angles and the average value of the diffraction intensity at a plurality of measurement points within the range of diffraction angles of 30.0° or more and less than 30.1° are calculated. Then, a straight line connecting two points of diffraction angle/diffraction intensity thus calculated is taken as a baseline. The average value of multiple measurement points for calculating the baseline from the viewpoint of measurement accuracy, that is, the average value of the measurement points of 10.0 ° or more and less than 10.1 °, and 30.0 ° or more and less than 30.1 ° It is desirable to use an average value of 5 or more points for each of the measurement points in the range. Moreover, when the weight of the sample used for measurement is 0.1 g or more, it is easy to obtain a highly accurate measurement value.
　フッ化ビニリデン重合体のＸ線回折パターンは、フッ化ビニリデン重合体の結晶化状態を表す。また、Ｘ線回折パターンの回折強度の極大値の位置は、結晶構造の種類によって異なる。 The X-ray diffraction pattern of a vinylidene fluoride polymer represents the crystallization state of the vinylidene fluoride polymer. Also, the position of the maximum value of the diffraction intensity in the X-ray diffraction pattern differs depending on the type of crystal structure.
　例えば、後述の実施例におけるフッ化ビニリデン重合体Ｄ（フッ化ビニリデンの単独重合体）のように、回折角度１０°以上３０°以下の領域に多数の極大値を有する場合、フッ化ビニリデン重合体が、多くの結晶構造を含んでいるといえる（図１参照）。このようなフッ化ビニリデン単独重合体を、溶媒に溶解させるためには、大きなエネルギーが必要となる。また本発明者らの検討によれば、特に、フッ化ビニリデン重合体が、回折角度２２．５°以上３０°以下の範囲に現れる結晶構造を多く含む場合に、後述の溶媒に対する溶解性が低いことが明らかとなった。 For example, when the vinylidene fluoride polymer D (homopolymer of vinylidene fluoride) in Examples described later has a large number of maxima in the diffraction angle region of 10° or more and 30° or less, the vinylidene fluoride polymer can be said to contain many crystal structures (see Fig. 1). A large amount of energy is required to dissolve such a vinylidene fluoride homopolymer in a solvent. Further, according to the study of the present inventors, especially when the vinylidene fluoride polymer contains many crystal structures appearing in the range of diffraction angles of 22.5° or more and 30° or less, the solubility in the solvent described later is low. It became clear.
　一方、後述の実施例におけるフッ化ビニリデン重合体Ｇのように、Ｘ線回折パターンに極大値を有さない場合には、フッ化ビニリデン重合体が結晶構造を有さず、ゴム質となる（図１参照）。このようなフッ化ビニリデン重合体では、その内部に溶媒が入り込み難く、フッ化ビニリデン重合体の溶媒に対する溶解性が低くなる。 On the other hand, when the vinylidene fluoride polymer G in Examples described later does not have a maximum value in the X-ray diffraction pattern, the vinylidene fluoride polymer does not have a crystal structure and becomes rubbery ( See Figure 1). In such a vinylidene fluoride polymer, it is difficult for the solvent to enter therein, and the solubility of the vinylidene fluoride polymer in the solvent is low.
　これに対し、回折角度が１０°以上１９．９°以下の範囲に少なくとも１つの極大値を有し、かつ回折角度２２．５°以上３０°以下の範囲における最大回折強度が、回折角度１０°以上１９．９°以下の範囲における最大回折強度以下であるフッ化ビニリデン重合体では、後述の溶媒に対する溶解性が格段に高くなる。このようなフッ化ビニリデン重合体では、上述の溶媒に対する溶解性が低い結晶構造が少なく、かつ適度に溶媒が入り込みやすいことから、溶媒に対する溶解性が高いと考えられる。 On the other hand, the diffraction angle has at least one maximum in the range of 10 ° or more and 19.9 ° or less, and the maximum diffraction intensity in the diffraction angle range of 22.5 ° or more and 30 ° or less is 10 °. A vinylidene fluoride polymer whose diffraction intensity is equal to or less than the maximum diffraction intensity in the range of 19.9° or less has remarkably high solubility in the solvent described later. Such a vinylidene fluoride polymer is considered to have a high solubility in solvents because it has few crystal structures with low solubility in the solvents described above and is moderately easily penetrated by the solvent.
　ここで、上記要件（Ｃ）を満たすフッ化ビニリデン重合体は、フッ化ビニリデン重合体中のフッ化ビニリデン由来の構造単位の量、および含フッ素アルキルビニル化合物由来の構造単位の量を上述の範囲に調整することで得られやすい。また、回折角度が１０°以上１９．９°以下の範囲に極大値が現れる結晶構造を崩さないような条件で、フッ化ビニリデン重合体を調製したり、調製後の処理を行ったりすることが好ましい。例えば上記結晶構造を崩す処理の例には、調製したフッ化ビニリデン重合体をアセトン等の溶媒に溶解させる処理が含まれる。 Here, the vinylidene fluoride polymer that satisfies the above requirement (C) has the amount of structural units derived from vinylidene fluoride in the vinylidene fluoride polymer and the amount of structural units derived from the fluorine-containing alkyl vinyl compound within the above ranges. can be easily obtained by adjusting the In addition, the vinylidene fluoride polymer may be prepared and post-preparation treatment may be performed under conditions that do not destroy the crystal structure in which the maximum diffraction angle appears in the range of 10° or more and 19.9° or less. preferable. For example, an example of the treatment for destroying the crystal structure includes a treatment of dissolving the prepared vinylidene fluoride polymer in a solvent such as acetone.
　上記要件（Ａ）～（Ｃ）を満たすフッ化ビニリデン重合体の重量平均分子量は、１００００以上２５０００００以下が好ましく、５００００以上２００００００以下がより好ましく、１０００００以上１５０００００以下がさらに好ましい。上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって測定される、ポリスチレン換算値である。フッ化ビニリデン重合体の重量平均分子量が上記範囲であると、フッ化ビニリデン重合体が後述の溶媒にさらに溶解しやすくなる。 The weight average molecular weight of the vinylidene fluoride polymer satisfying the above requirements (A) to (C) is preferably 10,000 to 2,500,000, more preferably 50,000 to 2,000,000, and even more preferably 100,000 to 1,500,000. The weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC). When the weight-average molecular weight of the vinylidene fluoride polymer is within the above range, the vinylidene fluoride polymer is more easily dissolved in the below-described solvent.
　なお、上述の要件（Ａ）～（Ｃ）を満たすフッ化ビニリデン重合体は、フッ化ビニリデンと、含フッ素アルキルビニル化合物と、必要に応じて他の化合物と、を公知の方法で共重合させて調製することができる。これらを共重合する方法の例には、懸濁重合、乳化重合、溶液重合等が含まれる。ここで、上述の要件（Ｂ）および要件（Ｃ）を満たすフッ化ビニリデン重合体が得られやすいという観点で乳化重合が好ましい。乳化重合によって共重合したフッ化ビニリデン重合体は一次粒子径が小さくなるので、分散しやすくなりかつ分散後の安定性が向上する。 The vinylidene fluoride polymer satisfying the above requirements (A) to (C) is obtained by copolymerizing vinylidene fluoride, a fluorine-containing alkyl vinyl compound, and, if necessary, other compounds by a known method. can be prepared by Examples of methods for copolymerizing these include suspension polymerization, emulsion polymerization, solution polymerization, and the like. Here, emulsion polymerization is preferable from the viewpoint that a vinylidene fluoride polymer that satisfies the requirements (B) and (C) described above can be easily obtained. Since the vinylidene fluoride polymer copolymerized by emulsion polymerization has a small primary particle size, it is easy to disperse and the stability after dispersion is improved.
　・溶媒
　フッ化ビニリデン重合体溶液が含む溶媒は、分子量１００以上であり、かつエーテル、ケトン、およびエステルから選択される少なくとも１種の構造を有する親和性溶媒を少なくとも含んでいればよく、本発明の目的および効果を損なわない範囲で、他の溶媒を一部に含んでいてもよい。ただし、溶媒全量に対する、親和性溶媒の量は、８０質量％以上が好ましく、９０質量％以上がより好ましい。 Solvent The solvent contained in the vinylidene fluoride polymer solution may contain at least an affinity solvent having a molecular weight of 100 or more and having at least one structure selected from ethers, ketones, and esters. Other solvents may be partially contained within a range that does not impair the purpose and effect of the above. However, the amount of the affinity solvent is preferably 80% by mass or more, more preferably 90% by mass or more, relative to the total amount of the solvent.
　上記親和性溶媒の分子量が１００以上であると、極性基であるエーテル、ケトン、およびエステルを有している溶媒であっても極性が適度に低下するため、上述のフッ化ビニリデン重合体との親和性が高まる。親和性溶媒の分子量は、１００以上２５１以下が好ましく、１００以上２０１以下がより好ましく、１００以上１６１以下がさらに好ましい。 When the molecular weight of the affinity solvent is 100 or more, the polarity of the solvent having ether, ketone, and ester polar groups is moderately lowered, so that the above-mentioned vinylidene fluoride polymer and Affinity increases. The molecular weight of the affinity solvent is preferably 100 or more and 251 or less, more preferably 100 or more and 201 or less, and even more preferably 100 or more and 161 or less.
　また、親和性溶媒は、エーテル、ケトン、およびエステルのうち、いずれか一つのみを有していてもよく、二種以上を含んでいてもよい。また、溶媒は、親和性溶媒を一種のみ含んでいてもよく、二種以上含んでいてもよい。 Also, the affinity solvent may contain only one of ether, ketone, and ester, or may contain two or more. Moreover, the solvent may contain only 1 type of affinity solvent, and may contain 2 or more types.
　ここで、上記親和性溶媒のオクタノール／水分配係数ＬｏｇＰは０以上が好ましく、０以上４以下がより好ましく、０以上３以下がさらに好ましく、０．５以上２．９以下がさらに好ましい。親和性溶媒のオクタノール／水分配係数が０以上であると、フッ化ビニリデン重合体溶液の含水性が低くなり、フッ化ビニリデン重合体溶液の安定性が高まりやすい。なお、オクタノール／水分配係数ＬｏｇＰは、オクタノールおよび水の二相系に親和性溶媒を溶解させ、２５℃で平衡状態としたときの、オクタノール相中の親和性溶媒の濃度Ｃｏ、および水相中の親和性の溶媒の濃度Ｃｗとの比の常用対数値（Ｌｏｇ（Ｃｏ／Ｃｗ））である。 Here, the octanol/water partition coefficient LogP of the affinity solvent is preferably 0 or more, more preferably 0 or more and 4 or less, even more preferably 0 or more and 3 or less, and even more preferably 0.5 or more and 2.9 or less. When the octanol/water partition coefficient of the affinity solvent is 0 or more, the water content of the vinylidene fluoride polymer solution becomes low, and the stability of the vinylidene fluoride polymer solution tends to increase. Note that the octanol/water partition coefficient LogP is the concentration Co of the affinity solvent in the octanol phase and is the common logarithm (Log(Co/Cw)) of the ratio of the affinity of the solvent to the concentration Cw of the solvent.
　ここで、親和性溶媒の具体例には、ジイソブチルケトン（分子量：１４２、ＬｏｇＰ：２．５６）、メチルイソブチルケトン（分子量：１００，ＬｏｇＰ：１．３１）、イソホロン（分子量：１３８、ＬｏｇＰ：１．６７）等のケトン；炭酸エチルメチル（分子量：１０４、ＬｏｇＰ：１．２１）、酢酸アミル（分子量：１３０、ＬｏｇＰ：２．１８）、酪酸エチル（分子量：１１６、ＬｏｇＰ：１．８５）、酪酸ブチル（分子量：１４４、ＬｏｇＰ：２．８）、酢酸イソプロピル（分子量：１０２、ＬｏｇＰ：１．３）、プロピオン酸エチル（分子量：１０２、ＬｏｇＰ：１．２１）等のエステル；酢酸２－ブトキシエチル（分子量：１６０、ＬｏｇＰ：１．５１）等のエステルおよびエーテルを含む溶媒等が含まれる。 Here, specific examples of the affinity solvent include diisobutyl ketone (molecular weight: 142, LogP: 2.56), methyl isobutyl ketone (molecular weight: 100, LogP: 1.31), isophorone (molecular weight: 138, LogP: 1 .67) and other ketones; ethyl methyl carbonate (molecular weight: 104, Log P: 1.21), amyl acetate (molecular weight: 130, Log P: 2.18), ethyl butyrate (molecular weight: 116, Log P: 1.85), Esters such as butyl butyrate (molecular weight: 144, LogP: 2.8), isopropyl acetate (molecular weight: 102, LogP: 1.3), ethyl propionate (molecular weight: 102, LogP: 1.21); 2-butoxy acetate Solvents including esters and ethers such as ethyl (molecular weight: 160, LogP: 1.51) and the like are included.
　上記の中でも取り扱い性の観点等から、親和性溶媒としては、イソホロン、ジイソブチルケトン、メチルイソブチルケトン、酢酸アミル、酢酸イソプロピル、酪酸エチル、酪酸ブチル、およびプロピオン酸エチルおよび、が好ましい。 Among the above, isophorone, diisobutyl ketone, methyl isobutyl ketone, amyl acetate, isopropyl acetate, ethyl butyrate, butyl butyrate, and ethyl propionate are preferable as the affinity solvent from the viewpoint of handleability.
　・その他の成分
　フッ化ビニリデン重合体溶液は、その用途に合わせて、かつ本発明の目的及び効果を損なわない範囲で、上記フッ化ビニリデン重合体および溶媒以外の成分を含んでいてもよい。例えばアクリル樹脂等の他の種類の樹脂や、無機フィラー等の充填剤、各種添加剤等をさらに含んでいてもよい。 • Other components The vinylidene fluoride polymer solution may contain components other than the vinylidene fluoride polymer and the solvent, depending on the application and within a range that does not impair the object and effect of the present invention. For example, other types of resins such as acrylic resins, fillers such as inorganic fillers, and various additives may be further included.
　・物性
　フッ化ビニリデン重合体溶液における、上記フッ化ビニリデン重合体の濃度は特に制限されないが、その濃度は３０質量％以下が好ましい。フッ化ビニリデン重合体の濃度が当該範囲であると、フッ化ビニリデン重合体の溶け残り等が生じ難く、さらにフッ化ビニリデン重合体の安定性が高まりやすい。さらに、フッ化ビニリデン重合体溶液を各種用途に使用しやすくなる。 - Physical property Although the concentration of the vinylidene fluoride polymer in the vinylidene fluoride polymer solution is not particularly limited, the concentration is preferably 30% by mass or less. When the concentration of the vinylidene fluoride polymer is within this range, it is difficult for the vinylidene fluoride polymer to remain undissolved, and the stability of the vinylidene fluoride polymer tends to increase. Furthermore, it becomes easy to use the vinylidene fluoride polymer solution for various purposes.
　フッ化ビニリデン重合体溶液のヘーズ値は１８％以下が好ましく、１５％以下がより好ましく、１０％以下がさらにより好ましい。フッ化ビニリデン重合体溶液のヘーズ値が１８％以下である場合、溶媒にフッ化ビニリデン重合体が十分に溶解しているといえる。また、当該ヘーズ値が１８％以下であると、時間が経過しても、フッ化ビニリデン重合体の沈殿や分離等が生じ難い。 The haze value of the vinylidene fluoride polymer solution is preferably 18% or less, more preferably 15% or less, and even more preferably 10% or less. When the haze value of the vinylidene fluoride polymer solution is 18% or less, it can be said that the vinylidene fluoride polymer is sufficiently dissolved in the solvent. Further, when the haze value is 18% or less, the vinylidene fluoride polymer is less likely to precipitate or separate over time.
　フッ化ビニリデン重合体溶液のヘーズ値は、ＩＳＯ　１４７８２に準拠した日本電色工業製のＮＤＨ２０００を用いて測定した。本明細書におけるヘーズ値とは、各フッ化ビニリデン重合体溶液を石英セルに入れ、の拡散光線透過率Ｔｄ（％）および全光線透過率Ｔｔ（％）を測定し、下記式に基づいて算出される値である。
　ヘーズ値＝（Ｔｄ／Ｔｔ）×１００（％） The haze value of the vinylidene fluoride polymer solution was measured using NDH2000 manufactured by Nippon Denshoku Industries based on ISO 14782. The haze value in this specification is calculated based on the following formula by measuring the diffuse light transmittance Td (%) and the total light transmittance Tt (%) by putting each vinylidene fluoride polymer solution in a quartz cell. is the value to be
Haze value = (Td/Tt) x 100 (%)
　・調製方法
　上記フッ化ビニリデン重合体溶液の調製方法は特に制限されず、フッ化ビニリデン重合体および溶媒を公知の方法で混合し、フッ化ビニリデン重合体を溶解させることで調製できる。フッ化ビニリデン重合体および溶媒は、４０℃以上１５０℃以下の温度で混合することが好ましく、当該温度は６０℃以上１００℃以下がより好ましい。温度が６０℃以上であると、フッ化ビニリデン重合体が軟化したり溶解したりしやすくなる。一方で、温度が１００℃以下であると、溶媒が過度に揮発したりし難く、所望の組成のフッ化ビニリデン重合体溶液が得られやすくなる。 - Preparation method The method for preparing the vinylidene fluoride polymer solution is not particularly limited, and it can be prepared by mixing the vinylidene fluoride polymer and a solvent by a known method and dissolving the vinylidene fluoride polymer. The vinylidene fluoride polymer and the solvent are preferably mixed at a temperature of 40° C. or higher and 150° C. or lower, more preferably 60° C. or higher and 100° C. or lower. When the temperature is 60° C. or higher, the vinylidene fluoride polymer tends to soften or dissolve. On the other hand, when the temperature is 100° C. or lower, the solvent is less likely to volatilize excessively, and a vinylidene fluoride polymer solution having a desired composition can be easily obtained.
　なお、フッ化ビニリデン重合体および溶媒を混合する際には、公知の装置により攪拌を行うことが好ましい。また、混合時間（攪拌時間）は、３分以上３時間以下が製造効率の観点で好ましく、５分以上２時間以下がより好ましい。なお、本発明では、上述の要件（Ａ）～（Ｃ）を満たすフッ化ビニリデン重合体と、上記親和性溶媒を含む溶媒とを組み合わせることから、フッ化ビニリデン重合体を溶媒に溶解させる際に時間がかからず、さらに得られるフッ化ビニリデン重合体溶液の安定性も良好にすることができる。 When mixing the vinylidene fluoride polymer and the solvent, it is preferable to stir using a known device. In addition, the mixing time (stirring time) is preferably 3 minutes or more and 3 hours or less from the viewpoint of production efficiency, and more preferably 5 minutes or more and 2 hours or less. In the present invention, a vinylidene fluoride polymer that satisfies the above requirements (A) to (C) is combined with a solvent containing the above-mentioned affinity solvent. Therefore, when the vinylidene fluoride polymer is dissolved in the solvent, It does not take much time, and the stability of the resulting vinylidene fluoride polymer solution can be improved.
　・用途
　上記フッ化ビニリデン重合体溶液の用途は特に制限されず、例えば塗料やコーティング剤、非水電解質二次電池や全固体電池の各種バインダ等、様々な用途に使用可能である。 - Use The use of the vinylidene fluoride polymer solution is not particularly limited, and it can be used for various uses such as paints, coating agents, and various binders for non-aqueous electrolyte secondary batteries and all-solid-state batteries.
　以下、本発明の具体的な実施例を比較例とともに説明するが、本発明はこれらに限定されるものではない。 Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to these.
　１．フッ化ビニリデン重合体の調製
　以下の方法によりフッ化ビニリデン重合体Ａ～Ｇを調製した。 1. Preparation of Vinylidene Fluoride Polymer Vinylidene fluoride polymers A to G were prepared by the following method.
　・フッ化ビニリデン重合体Ａの調製
　オートクレーブに０．２質量部のリン酸水素二ナトリウム（Ｎａ２ＨＰＯ４）と、３３０質量部の水とを入れた。脱気後、０．００３質量部のポリオキシエチレンアルキレンアルキルエーテルと、０．１質量部の酢酸エチルと、８．７質量部のフッ化ビニリデン（ＶＤＦ）と、３８．０質量部のヘキサフルオロプロピレン（ＨＦＰ）とを入れた。そして、オートクレーブ内の温度を、攪拌下で８０℃に昇温し、０．０６質量部の過硫酸アンモニウム（ＡＰＳ）を入れて重合を開始させた。この時の初期圧力は２．５ＭＰａであり、圧力が２．５ＭＰａのまま維持されるように連続的に５３．３質量部のＶＤＦを添加した。その後、圧力が１．５ＭＰａまで下がったところで重合反応の終了とし、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体（ＶＤＦ－ＨＦＰ共重合体）のラテックスを得た。 - Preparation of vinylidene fluoride polymer A 0.2 parts by mass of disodium hydrogen phosphate (Na2HPO4) and 330 parts by mass of water were placed in an autoclave. After degassing, 0.003 parts by weight of polyoxyethylene alkylene alkyl ether, 0.1 parts by weight of ethyl acetate, 8.7 parts by weight of vinylidene fluoride (VDF), and 38.0 parts by weight of hexafluoro Propylene (HFP) was added. Then, the temperature inside the autoclave was raised to 80° C. while stirring, and 0.06 parts by mass of ammonium persulfate (APS) was added to initiate polymerization. The initial pressure at this time was 2.5 MPa, and 53.3 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa. After that, the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
　当該ラテックスの樹脂濃度は、２０．６質量％であり、当該ラテックス中のＶＤＦ－ＨＦＰ共重合体の平均粒子径は２２１ｎｍであった。ＶＤＦ－ＨＦＰ共重合体の平均粒子径は、Ｂｅｃｋｍａｎ　Ｃｏｕｌｔｅｒ社のＤｅｌｓａＭａｘＣＯＲＥ（検出器角度は９０度）を用い、５０回の積算により導出した値である。 The resin concentration of the latex was 20.6% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 221 nm. The average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees).
　その後、当該ラテックスを液体窒素で凍結させ、さらに凍結乾燥機を用いて３０．０Ｐａ以下の減圧下で８時間真空乾燥させて、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体の粒子（フッ化ビニリデン重合体Ａ）を得た。なお、１９Ｆ－ＮＭＲにより導出したフッ化ビニリデンとヘキサフルオロプロピレンとの質量比は、６３：３７であった。 Thereafter, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (fluoride A vinylidene polymer A) was obtained. The mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 63:37.
　・フッ化ビニリデン重合体Ｂの調製
　オートクレーブに０．２質量部のリン酸水素二ナトリウム（Ｎａ２ＨＰＯ４）と、３３０質量部の水とを入れた。脱気後、０．００３質量部のポリオキシエチレンアルキレンアルキルエーテルと、０．１質量部の酢酸エチルと、５質量部のフッ化ビニリデン（ＶＤＦ）と、４７．０質量部のヘキサフルオロプロピレン（ＨＦＰ）とを入れた。そして、オートクレーブ内の温度を、攪拌下で８０℃に昇温し、０．３質量部の過硫酸アンモニウム（ＡＰＳ）を入れて重合を開始させた。この時の初期圧力は２．５ＭＰａであり、圧力が２．５ＭＰａのまま維持されるように連続的に４８質量部のＶＤＦを添加した。その後、圧力が１．５ＭＰａまで下がったところで重合反応の終了とし、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体（ＶＤＦ－ＨＦＰ共重合体）のラテックスを得た。 - Preparation of vinylidene fluoride polymer B 0.2 parts by mass of disodium hydrogen phosphate (Na2HPO4) and 330 parts by mass of water were placed in an autoclave. After degassing, 0.003 parts by weight of polyoxyethylene alkylene alkyl ether, 0.1 parts by weight of ethyl acetate, 5 parts by weight of vinylidene fluoride (VDF), and 47.0 parts by weight of hexafluoropropylene ( HFP) was added. Then, the temperature inside the autoclave was raised to 80° C. while stirring, and 0.3 parts by mass of ammonium persulfate (APS) was added to initiate polymerization. The initial pressure at this time was 2.5 MPa, and 48 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa. After that, the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
　当該ラテックスの樹脂濃度は、２０．６質量％であり、当該ラテックス中のＶＤＦ－ＨＦＰ共重合体の平均粒子径は１００ｎｍであった。ＶＤＦ－ＨＦＰ共重合体の平均粒子径は、Ｂｅｃｋｍａｎ　Ｃｏｕｌｔｅｒ社のＤｅｌｓａＭａｘＣＯＲＥ（検出器角度は９０度）を用い、５０回の積算により導出した値である。
　その後、当該ラテックスを液体窒素で凍結させ、さらに凍結乾燥機を用いて３０．０Ｐａ以下の減圧下で８時間真空乾燥させて、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体の粒子（フッ化ビニリデン重合体Ｂ）を得た。なお、１９Ｆ－ＮＭＲにより導出したフッ化ビニリデンとヘキサフルオロプロピレンとの質量比は、５５：４５であった。 The resin concentration of the latex was 20.6% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 100 nm. The average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees).
Thereafter, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (fluoride A vinylidene polymer B) was obtained. The mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 55:45.
　・フッ化ビニリデン重合体Ｃの調製
　オートクレーブに０．２質量部のリン酸水素二ナトリウム（Ｎａ２ＨＰＯ４）と、３３０質量部の水とを入れた。脱気後、０．００３質量部のポリオキシエチレンアルキレンアルキルエーテルと、０．１質量部の酢酸エチルと、１３質量部のフッ化ビニリデン（ＶＤＦ）と、２４質量部のヘキサフルオロプロピレン（ＨＦＰ）とを入れた。そして、オートクレーブ内の温度を、攪拌下で８０℃に昇温し、０．０６質量部の過硫酸アンモニウム（ＡＰＳ）を入れて重合を開始させた。この時の初期圧力は２．５ＭＰａであり、圧力が２．５ＭＰａのまま維持されるように連続的に６３質量部のＶＤＦを添加した。その後、圧力が１．５ＭＰａまで下がったところで重合反応の終了とし、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体（ＶＤＦ－ＨＦＰ共重合体）のラテックスを得た。 - Preparation of vinylidene fluoride polymer C 0.2 parts by mass of disodium hydrogen phosphate (Na2HPO4) and 330 parts by mass of water were placed in an autoclave. After degassing, 0.003 parts by weight of polyoxyethylene alkylene alkyl ether, 0.1 parts by weight of ethyl acetate, 13 parts by weight of vinylidene fluoride (VDF), and 24 parts by weight of hexafluoropropylene (HFP) and Then, the temperature inside the autoclave was raised to 80° C. while stirring, and 0.06 parts by mass of ammonium persulfate (APS) was added to initiate polymerization. At this time, the initial pressure was 2.5 MPa, and 63 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa. After that, the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
　当該ラテックスの樹脂濃度は、２０．９質量％であり、当該ラテックス中のＶＤＦ－ＨＦＰ共重合体の平均粒子径は１８０ｎｍであった。ＶＤＦ－ＨＦＰ共重合体の平均粒子径は、Ｂｅｃｋｍａｎ　Ｃｏｕｌｔｅｒ社のＤｅｌｓａＭａｘＣＯＲＥ（検出器角度は９０度）を用い、５０回の積算により導出した値である。
　その後、当該ラテックスを液体窒素で凍結させ、さらに凍結乾燥機を用いて３０．０Ｐａ以下の減圧下で８時間真空乾燥させて、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体の粒子（フッ化ビニリデン重合体Ｃ）を得た。なお、１９Ｆ－ＮＭＲにより導出したフッ化ビニリデンとヘキサフルオロプロピレンとの質量比は、８０：２０であった。 The resin concentration of the latex was 20.9% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 180 nm. The average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees).
Thereafter, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (fluoride A vinylidene polymer C) was obtained. The mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 80:20.
　・フッ化ビニリデン重合体Ｄの調製
　オートクレーブに０．２質量部のリン酸水素二ナトリウム（Ｎａ２ＨＰＯ４）と、３３０質量部の水とを入れた。脱気後、０．００３質量部のポリオキシエチレンアルキレンアルキルエーテルと、０．１質量部の酢酸エチルと、３０質量部のフッ化ビニリデン（ＶＤＦ）とを入れた。そして、オートクレーブ内の温度を、攪拌下で８０℃に昇温し、０．０６質量部の過硫酸アンモニウム（ＡＰＳ）を入れて重合を開始させた。この時の初期圧力は２．５ＭＰａであり、圧力が２．５ＭＰａのまま維持されるように連続的に７０質量部のＶＤＦを添加した。その後、圧力が１．５ＭＰａまで下がったところで重合反応の終了とし、フッ化ビニリデンの単独重合体（ＶＤＦ単独重合体）のラテックスを得た。 - Preparation of vinylidene fluoride polymer D 0.2 parts by mass of disodium hydrogen phosphate (Na2HPO4) and 330 parts by mass of water were placed in an autoclave. After degassing, 0.003 parts by weight of polyoxyethylene alkylene alkyl ether, 0.1 parts by weight of ethyl acetate, and 30 parts by weight of vinylidene fluoride (VDF) were added. Then, the temperature inside the autoclave was raised to 80° C. while stirring, and 0.06 parts by mass of ammonium persulfate (APS) was added to initiate polymerization. The initial pressure at this time was 2.5 MPa, and 70 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa. After that, the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of vinylidene fluoride homopolymer (VDF homopolymer) was obtained.
　当該ラテックスの樹脂濃度は、２０．９質量％であり、当該ラテックス中のＶＤＦ単独重合体の平均粒子径は１５０ｎｍであった。ＶＤＦ単独重合体の平均粒子径は、Ｂｅｃｋｍａｎ　Ｃｏｕｌｔｅｒ社のＤｅｌｓａＭａｘＣＯＲＥ（検出器角度は９０度）を用い、５０回の積算により導出した値である。
　その後、当該ラテックスを液体窒素で凍結させ、さらに凍結乾燥機を用いて３０．０Ｐａ以下の減圧下で８時間真空乾燥させて、フッ化ビニリデン単独重合体の粒子（フッ化ビニリデン単独重合体Ｄ）を得た。 The resin concentration of the latex was 20.9% by mass, and the average particle diameter of the VDF homopolymer in the latex was 150 nm. The average particle size of the VDF homopolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees).
After that, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain vinylidene fluoride homopolymer particles (vinylidene fluoride homopolymer D). got
　・フッ化ビニリデン重合体Ｅの調製
　オートクレーブに０．３質量部のリン酸水素二ナトリウム（Ｎａ２ＨＰＯ４）と、３８０質量部の水とを入れた。脱気後、０．００３質量部のポリオキシエチレンアルキレンアルキルエーテルと、０．１質量部の酢酸エチルと、２５質量部のフッ化ビニリデン（ＶＤＦ）と、１０質量部のヘキサフルオロプロピレン（ＨＦＰ）とを入れた。そして、オートクレーブ内の温度を、攪拌下で８０℃に昇温し、０．２質量部の過硫酸アンモニウム（ＡＰＳ）を入れて重合を開始させた。この時の初期圧力は４．０１ＭＰａであり、圧力が２．５ＭＰａのまま維持されるように連続的に６５質量部のＶＤＦを添加した。その後、圧力が１．５ＭＰａまで下がったところで重合反応の終了とし、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体（ＶＤＦ－ＨＦＰ共重合体）のラテックスを得た。 - Preparation of vinylidene fluoride polymer E 0.3 parts by mass of disodium hydrogen phosphate (Na2HPO4) and 380 parts by mass of water were placed in an autoclave. After degassing, 0.003 parts by weight of polyoxyethylene alkylene alkyl ether, 0.1 parts by weight of ethyl acetate, 25 parts by weight of vinylidene fluoride (VDF), and 10 parts by weight of hexafluoropropylene (HFP) and Then, the temperature inside the autoclave was raised to 80° C. while stirring, and 0.2 parts by mass of ammonium persulfate (APS) was added to initiate polymerization. At this time, the initial pressure was 4.01 MPa, and 65 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa. After that, the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
　当該ラテックスの樹脂濃度は、２０．９質量％であり、当該ラテックス中のＶＤＦ－ＨＦＰ共重合体の平均粒子径は１２９ｎｍであった。ＶＤＦ－ＨＦＰ共重合体の平均粒子径は、Ｂｅｃｋｍａｎ　Ｃｏｕｌｔｅｒ社のＤｅｌｓａＭａｘＣＯＲＥ（検出器角度は９０度）を用い、５０回の積算により導出した値である。
　その後、当該ラテックスを液体窒素で凍結させ、さらに凍結乾燥機を用いて３０．０Ｐａ以下の減圧下で８時間真空乾燥させて、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体の粒子（フッ化ビニリデン重合体Ｅ）を得た。なお、１９Ｆ－ＮＭＲにより導出したフッ化ビニリデンとヘキサフルオロプロピレンとの質量比は、９１：９であった。 The resin concentration of the latex was 20.9% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 129 nm. The average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees).
Thereafter, the latex is frozen with liquid nitrogen, and further vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (fluoride A vinylidene polymer E) was obtained. The mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 91:9.
　・フッ化ビニリデン重合体Ｆの調製
　オートクレーブに０．２質量部のリン酸水素二ナトリウム（Ｎａ２ＨＰＯ４）と、３３０質量部の水とを入れた。脱気後、０．００３質量部のポリオキシエチレンアルキレンアルキルエーテルと、０．２質量部の酢酸エチルと、８質量部のフッ化ビニリデン（ＶＤＦ）と、３２質量部のヘキサフルオロプロピレン（ＨＦＰ）とを入れた。そして、オートクレーブ内の温度を、攪拌下で８０℃に昇温し、０．３質量部の過硫酸アンモニウム（ＡＰＳ）を入れて重合を開始させた。この時の初期圧力は２．５ＭＰａであり、圧力が２．５ＭＰａのまま維持されるように連続的に６０質量部のＶＤＦを添加した。その後、圧力が１．５ＭＰａまで下がったところで重合反応の終了とし、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体（ＶＤＦ－ＨＦＰ共重合体）のラテックスを得た。 - Preparation of vinylidene fluoride polymer F 0.2 parts by mass of disodium hydrogen phosphate (Na2HPO4) and 330 parts by mass of water were placed in an autoclave. After degassing, 0.003 parts by weight of polyoxyethylene alkylene alkyl ether, 0.2 parts by weight of ethyl acetate, 8 parts by weight of vinylidene fluoride (VDF), and 32 parts by weight of hexafluoropropylene (HFP) and Then, the temperature inside the autoclave was raised to 80° C. while stirring, and 0.3 parts by mass of ammonium persulfate (APS) was added to initiate polymerization. At this time, the initial pressure was 2.5 MPa, and 60 parts by mass of VDF was continuously added so that the pressure was maintained at 2.5 MPa. After that, the polymerization reaction was terminated when the pressure decreased to 1.5 MPa, and a latex of a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP copolymer) was obtained.
　当該ラテックスの樹脂濃度は、２０．９質量％であり、当該ラテックス中のＶＤＦ－ＨＦＰ共重合体の平均粒子径は２１０ｎｍであった。ＶＤＦ－ＨＦＰ共重合体の平均粒子径は、Ｂｅｃｋｍａｎ　Ｃｏｕｌｔｅｒ社のＤｅｌｓａＭａｘＣＯＲＥ（検出器角度は９０度）を用い、５０回の積算により導出した値である。
　その後、当該ラテックスを液体窒素で凍結させ、さらに凍結乾燥機を用いて３０．０Ｐａ以下の減圧下で８時間真空乾燥させて、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体の粒子を得た。この共重合体造粒粒子を共重合体造粒粒子１質量部に対して５質量部のアセトンを加えて溶解させた。このアセトン溶液にヘキサン１０質量部を加えて撹拌したのちろ別することでゴム状の沈殿物を得た。このゴム状沈殿物を真空乾燥機で乾燥させることでフッ化ビニリデンとヘキサフルオロプロピレンとの共重合体の粒子（フッ化ビニリデン重合体Ｆ）を得た。なお、１９Ｆ－ＮＭＲにより導出したフッ化ビニリデンとヘキサフルオロプロピレンとの質量比は、７０：３０であった。 The resin concentration of the latex was 20.9% by mass, and the average particle size of the VDF-HFP copolymer in the latex was 210 nm. The average particle size of the VDF-HFP copolymer is a value derived by accumulating 50 times using Beckman Coulter's DelsaMaxCORE (detector angle is 90 degrees).
After that, the latex was frozen with liquid nitrogen and vacuum-dried for 8 hours under a reduced pressure of 30.0 Pa or less using a freeze dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene. . The granulated copolymer particles were dissolved by adding 5 parts by mass of acetone to 1 part by mass of the granulated copolymer particles. 10 parts by mass of hexane was added to this acetone solution, and the mixture was stirred and separated by filtration to obtain a rubber-like precipitate. The rubber-like precipitate was dried in a vacuum dryer to obtain particles of a copolymer of vinylidene fluoride and hexafluoropropylene (vinylidene fluoride polymer F). The mass ratio of vinylidene fluoride and hexafluoropropylene derived by 19 F-NMR was 70:30.
　・フッ化ビニリデン重合体Ｇの調製
　撹拌機と外部に温度調節用ジャケットとを有する容積５Ｌのオートクレーブに、脱イオン、脱酸素処理した水１ｋｇと、過硫酸アンモニウム２．４ｇと、パーフルオロオクタン酸アンモニウム４．０ｇと、酸性亜硫酸ナトリウム０．８ｇとを仕込み、さらに水酸化ナトリウム０．２ｇを加えた。オートクレーブ内部を窒素ガスで３回置換した後、フッ化ビニリデン（ＶＤＦ）１７０ｇ、テトラフルオロエチレン（ＴＦＥ）８０ｇおよびヘキサフルオロプロピレン（ＨＦＰ）９０ｇを仕込み、撹拌しながら６０℃で７時間重合させた。重合物を凝固させ、ポリマーをろ別し、水洗した後、ｎ－へキサンにて洗浄を行い、さらにこれを真空乾燥機にて乾燥し、白色粉末状のフッ化ビニリデン重合体Ｇ　１６０ｇを得た。当該フッ化ビニリデン重合体Ｇの組成は、ＶＤＦ：ＴＦＥ：ＨＦＰ（質量比）が６１：２４：１５であった。 Preparation of vinylidene fluoride polymer G In a 5 L autoclave equipped with a stirrer and an external temperature control jacket, 1 kg of deionized and deoxygenated water, 2.4 g of ammonium persulfate, and ammonium perfluorooctanoate were added. 4.0 g and 0.8 g of sodium acid sulfite were charged, and 0.2 g of sodium hydroxide was added. After purging the inside of the autoclave with nitrogen gas three times, 170 g of vinylidene fluoride (VDF), 80 g of tetrafluoroethylene (TFE) and 90 g of hexafluoropropylene (HFP) were charged and polymerized at 60° C. for 7 hours while stirring. The polymer was coagulated, the polymer was separated by filtration, washed with water, washed with n-hexane, and dried in a vacuum dryer to obtain 160 g of white powdery vinylidene fluoride polymer G. rice field. The composition of the vinylidene fluoride polymer G was VDF:TFE:HFP (mass ratio) of 61:24:15.
　・フッ化ビニリデン重合体の物性の測定
　上記方法で得られたフッ化ビニリデン重合体Ａ～Ｇについて、以下の方法に基づき、ＤＳＣ曲線およびＸ線回折パターンを得た。 Measurement of physical properties of vinylidene fluoride polymer For the vinylidene fluoride polymers A to G obtained by the above method, DSC curves and X-ray diffraction patterns were obtained based on the following methods.
　（ＤＳＣ曲線）
　各フッ化ビニリデン重合体について、ＡＳＴＭ　Ｄ３４１８に準拠して、メトラー社製ＳＴＡＲｅ　ＤＳＣ１（装置）により、２０℃から２３０°の範囲について示差走査熱量測定を行い、ＤＳＣ曲線を作成した。昇温速度は１０℃／ｍｉｎ、５０ｍＬ／ｍｉｎの窒素フロー下で測定を実施した。
　また、ベースラインに対して吸熱側に凸である測定値群をピークとみなし、測定値群がなす曲線の極大値に相当する測定値をピークトップとした。なお、ベースラインは、以下のように特定した。
　４０℃以上４１℃以下の範囲にある３点の測定点と、１２０℃以上１２１℃以下の範囲にある３点の測定点について、それぞれの温度区間における熱流束の平均値と温度の平均値とを算出した。このように算出された４０℃以上４１℃以下の範囲にある各測定点の平均値と、１２０℃以上１２１℃以下の範囲にある各測定点の平均値の２点を結ぶ直線をベースラインとした。 (DSC curve)
For each vinylidene fluoride polymer, differential scanning calorimetry was performed in the range from 20° C. to 230° in accordance with ASTM D3418 using a Mettler STARe DSC1 (apparatus) to create a DSC curve. The measurement was performed under a temperature elevation rate of 10° C./min and a nitrogen flow of 50 mL/min.
A group of measured values convex to the endothermic side with respect to the baseline was regarded as a peak, and a measured value corresponding to the maximum value of a curve formed by the group of measured values was defined as the peak top. The baseline was specified as follows.
For the three measurement points in the range of 40° C. or higher and 41° C. or lower and the three measurement points in the range of 120° C. or higher and 121° C. or lower, the average value of the heat flux and the average value of the temperature in each temperature section was calculated. A straight line connecting two points of the average value of each measurement point in the range of 40 ° C. or higher and 41 ° C. or lower calculated in this way and the average value of each measurement point in the range of 120 ° C. or higher and 121 ° C. or lower is defined as the baseline. bottom.
　（Ｘ線回折測定）
　装置としては、フィリップス社製Ｘ‘Ｐｅｒｔ―ＰＲＯを用いた。光学系はブラッグ・ブレンターノ型集中光学系、Ｘ線の発生にはＣｕ管球を用いて、電圧値は４５ｋＶ、電流値は４０ｍＡとした。Ｘ線はＮｉフィルターを用いて単色化しており、可動スリット（照射面積は１ｃｍ×１ｃｍ）を用いた。サンプルの固定が必要な場合には、ポリイミドカプトンテープを用いた。
　上記のような装置条件のもと、ＪＩＳＫ０１３１：１９９６に基づいて各フッ化ビニリデン重合体のＸ線回折測定を行った。各測定における測定範囲は１０．００°から６０．００°、スキャンステップ数は１°あたり０．０２６とし、Ｔｉｍｅ　ｐｅｒ　ｓｔｅｐは８６．１９／秒とした。また、各フッ化ビニリデン重合体のＸ線回折パターンを図１に示す。得られたＸ線回折パターンにおいて、回折角度が１０°以上１９．９°以下の範囲に極大値があるか、および回折角度２２．５°以上３０°以下の範囲における最大回折強度が、回折角度１０°以上１９．９°以下の範囲における最大回折強度以下であるか、を確認した。 (X-ray diffraction measurement)
As an apparatus, Philips X'Pert-PRO was used. The optical system was a Bragg-Brentano concentrated optical system, a Cu tube was used to generate X-rays, the voltage value was 45 kV, and the current value was 40 mA. The X-ray was monochromatic using a Ni filter, and a movable slit (irradiation area: 1 cm x 1 cm) was used. Polyimide Kapton tape was used when sample fixation was required.
X-ray diffraction measurement of each vinylidene fluoride polymer was performed based on JISK0131:1996 under the apparatus conditions as described above. The measurement range in each measurement was 10.00° to 60.00°, the number of scanning steps was 0.026 per 1°, and the Time per step was 86.19/sec. FIG. 1 shows the X-ray diffraction pattern of each vinylidene fluoride polymer. In the obtained X-ray diffraction pattern, whether there is a maximum value in the diffraction angle range of 10 ° or more and 19.9 ° or less and the maximum diffraction intensity in the diffraction angle range of 22.5 ° or more and 30 ° or less is determined by the diffraction angle It was confirmed whether the diffraction intensity was equal to or less than the maximum diffraction intensity in the range of 10° or more and 19.9° or less.
　具体的には、Ｘ線回折測定における回折角度１０．０°以上１０．１°未満の範囲にある複数の測定点の回折角度の平均値および回折強度の平均値をそれぞれ算出した。同様に回折角度３０．０°以上３０．１°未満の範囲にある複数の測定点の回折角度の平均値および回折強度の平均値をそれぞれ算出した。そして、このように算出された回折角度・回折強度の値２点を結ぶ直線をベースラインとした。そして、当該ベースライン上の点の回折強度と、同一の回折角度におけるＸ線回折パターン上の回折強度とを比較し、Ｘ線回折パターン上の回折強度が連続して５点以上、ベースライン上の回折強度の１．５倍以上の値を示す場合に、当該Ｘ線回折パターンがピークを有すると判断した。さらに、Ｘ線回折パターン上の回折強度が連続して５点以上、ベースライン上の回折強度の１．５倍以上となる測定値群における極大値を特定し、当該極大値が、回折角度１０°以上１９．９°以下の範囲に入るかを特定した。 Specifically, the average value of the diffraction angle and the average value of the diffraction intensity at a plurality of measurement points in the range of diffraction angles of 10.0° or more and less than 10.1° in the X-ray diffraction measurement were calculated. Similarly, the average value of the diffraction angles and the average value of the diffraction intensity at a plurality of measurement points within the range of diffraction angles of 30.0° or more and less than 30.1° were calculated. A straight line connecting two points of diffraction angle and diffraction intensity thus calculated was used as a baseline. Then, the diffraction intensity at the points on the baseline is compared with the diffraction intensity on the X-ray diffraction pattern at the same diffraction angle. The X-ray diffraction pattern was judged to have a peak when the value was 1.5 times or more the diffraction intensity of . Furthermore, the maximum value in the measured value group at which the diffraction intensity on the X-ray diffraction pattern is continuously 5 points or more and the diffraction intensity on the baseline is 1.5 times or more is specified, and the maximum value is at a diffraction angle of 10. It was specified whether it falls within the range of 19.9° or less.
　当該特定方法によると、例えばフッ化ビニリデン重合体ＦやＧのＸ線回折パターンは回折角度１０°以上１９．９°以下の範囲に、測定値の回折強度が対応するベースラインの回折強度の１．５倍以上となる点が存在しないことから、極大値がないと判断した。結果を表１に示す。 According to the identification method, for example, the X-ray diffraction patterns of the vinylidene fluoride polymers F and G are in the range of diffraction angles of 10 ° or more and 19.9 ° or less, and the diffraction intensity of the measured value is 1 of the baseline diffraction intensity corresponding to It was judged that there was no maximum value because there was no point where the value was 0.5 times or more. Table 1 shows the results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　２．フッ化ビニリデン重合体溶液の調製
　２－１．溶媒の準備
　以下の表２に示す物性の溶媒を準備した。表２に示す各物性値は文献値である。
Figure JPOXMLDOC01-appb-T000002
 2. Preparation of vinylidene fluoride polymer solution 2-1. Preparation of Solvent A solvent having physical properties shown in Table 2 below was prepared. Each physical property value shown in Table 2 is a literature value.
Figure JPOXMLDOC01-appb-T000002
　２－２．フッ化ビニリデン重合体溶液の調製
　上記フッ化ビニリデン重合体と、上記溶媒とを、表３および表４に示す組み合わせで混合し、フッ化ビニリデン重合体溶液を得た。なお、フッ化ビニリデン重合体および溶媒を、７０℃、７００ｒｐｍで３時間撹拌して混合した。このときの溶液中のフッ化ビニリデン重合体の濃度を、溶液濃度として表す。そして、当該フッ化ビニリデン重合体溶液について、溶液の状態、ヘーズ値、および流動性を以下のように測定した。結果を表３および表４に示す。 2-2. Preparation of Vinylidene Fluoride Polymer Solution The above vinylidene fluoride polymer and the above solvent were mixed in the combinations shown in Tables 3 and 4 to obtain vinylidene fluoride polymer solutions. The vinylidene fluoride polymer and the solvent were mixed by stirring at 70° C. and 700 rpm for 3 hours. The concentration of the vinylidene fluoride polymer in the solution at this time is expressed as the solution concentration. Then, the state of the solution, the haze value, and the fluidity of the vinylidene fluoride polymer solution were measured as follows. The results are shown in Tables 3 and 4.
　（溶液の状態）
　各フッ化ビニリデン重合体溶液を目視で確認し、分離や白濁、沈殿、ゲル化が生じていないかを確認した。 (state of solution)
Each vinylidene fluoride polymer solution was visually observed to check for separation, cloudiness, precipitation, and gelation.
　（ヘーズの測定）
　日本電色工業製のＮＤＨ２０００でヘーズを測定した。各フッ化ビニリデン重合体溶液を石英セルに入れ、の拡散光線透過率Ｔｄ（％）および全光線透過率Ｔｔ（％）を測定し、ヘーズ値を以下のように算出した。
　ヘーズ値＝（Ｔｄ／Ｔｔ）×１００（％）
　測定の際には、各実施例、各比較例で使用している溶媒のヘーズを０とし、サンプルのヘーズを導出した。
　サンプルに分離が見られる場合や、未溶解の状態である場合には正確なヘーズを導出することが出来ないため、測定不可（表４では「－」と示す）とした。 (Haze measurement)
Haze was measured with NDH2000 manufactured by Nippon Denshoku Industries. Each vinylidene fluoride polymer solution was placed in a quartz cell, the diffuse light transmittance Td (%) and the total light transmittance Tt (%) were measured, and the haze value was calculated as follows.
Haze value = (Td/Tt) x 100 (%)
At the time of measurement, the haze of the solvent used in each example and each comparative example was assumed to be 0, and the haze of the sample was derived.
When separation was observed in the sample or when it was in an undissolved state, it was impossible to measure the haze (indicated by "-" in Table 4) because accurate haze could not be derived.
　（流動性）
　各フッ化ビニリデン重合体溶液をスクリュー瓶に加え、スクリュー瓶を４５度の角度まで傾けた。傾けたスクリュー瓶内部のフッ化ビニリデン重合体溶液に水平面が見られるかを、下記判断基準に基づき目視で確認した。
　〇：水平面が確認でき、かつ相分離や沈降が見られなかった
　×：水平面が確認できなかった、もしくは水平面が確認された場合であってもフッ化ビニリデン重合体溶液中に相分離が起こり、部分的に沈降が生じていた (Liquidity)
Each vinylidene fluoride polymer solution was added to a screw bottle and the screw bottle was tilted to an angle of 45 degrees. Whether or not the vinylidene fluoride polymer solution inside the tilted screw bottle had a horizontal surface was visually confirmed based on the following criteria.
○: A horizontal plane could be confirmed, and no phase separation or sedimentation was observed ×: A horizontal plane could not be confirmed, or even if a horizontal plane was confirmed, phase separation occurred in the vinylidene fluoride polymer solution, There was partial sedimentation
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上記表３に示されるように、上述の要件（Ａ）～（Ｃ）を満たすフッ化ビニリデン重合体と、上述の親和性溶媒を含む溶媒とを組み合わせた場合には、得られたフッ化ビニリデン重合体溶液が透明であり、かつ流動性も良好であった。さらにヘーズ値も低かった（実施例１～２１）。なお、表４に示されるように、フッ化ビニリデン重合体が、上記要件（Ａ）～（Ｃ）を満たしたとしても、溶媒が親和性溶媒を含まない場合、具体的には溶媒の分子量が１００未満である場合には、エーテル、ケトン、エステルを持つ溶媒であっても、極性が過度に高く上述のポリマーとの親和性が低いために一次粒子が凝集し、白濁が生じた（比較例１１）。また、分子量が１００以上の溶媒であっても、エーテル、ケトン、エステルのいずれも含まない溶媒は、極性が過度に低くポリマーが溶解しなかった（比較例１７，１８）。 As shown in Table 3 above, when a vinylidene fluoride polymer satisfying the above requirements (A) to (C) is combined with a solvent containing the above-mentioned affinity solvent, the resulting vinylidene fluoride The polymer solution was transparent and had good fluidity. Furthermore, the haze value was also low (Examples 1 to 21). As shown in Table 4, even if the vinylidene fluoride polymer satisfies the above requirements (A) to (C), when the solvent does not contain an affinity solvent, specifically the molecular weight of the solvent is If it is less than 100, even if the solvent has ether, ketone, or ester, the polarity is too high and the affinity with the above polymer is low, so the primary particles aggregate and cloudiness occurs (Comparative Example 11). Moreover, even if the solvent had a molecular weight of 100 or more, the solvent containing neither ether, ketone, nor ester had excessively low polarity and did not dissolve the polymer (Comparative Examples 17 and 18).
　また、要件（Ａ）を満たさないフッ化ビニリデン重合体Ｄを用いた比較例２、７、１３、２０、２３では、沈殿や分離が生じやすかった。溶媒と十分に相溶しなかったことが一因として考えられる。また、要件（Ａ）を満たしたとしても、要件（Ｂ）を満たさないフッ化ビニリデン重合体ＣまたはＥを用いた比較例１、３、６、８、１２、１４、１９、２５では、ゲル化や分離が生じた。この場合も、溶媒と十分に相溶できなかったと考えられる。さらに、要件（Ａ）および（Ｂ）は満たすものの、要件（Ｃ）を満たさないフッ化ビニリデン重合体Ｆや、要件（Ｂ）および（Ｃ）を満たさないフッ化ビニリデン重合体Ｇを用いた比較例４、５、９、１０、１５、１６、２１、２２、２４、２６では、溶媒によっては未溶解物が生じた。フッ化ビニリデン重合体ＦやＧはゴム質状であり、溶媒が内部に入り込みにくかったことが一因として考えられる。 In addition, in Comparative Examples 2, 7, 13, 20, and 23 using the vinylidene fluoride polymer D that did not satisfy the requirement (A), precipitation and separation were likely to occur. One possible reason is that it was not sufficiently compatible with the solvent. In Comparative Examples 1, 3, 6, 8, 12, 14, 19, and 25 using vinylidene fluoride polymer C or E, which does not satisfy requirement (B) even if requirement (A) is satisfied, gel separation and separation occurred. Also in this case, it is considered that the compound was not sufficiently compatible with the solvent. Furthermore, a comparison using a vinylidene fluoride polymer F that satisfies the requirements (A) and (B) but does not satisfy the requirement (C) and a vinylidene fluoride polymer G that does not satisfy the requirements (B) and (C) In Examples 4, 5, 9, 10, 15, 16, 21, 22, 24 and 26, undissolved substances were generated depending on the solvent. One reason for this is considered to be that the vinylidene fluoride polymers F and G are rubber-like, and it is difficult for the solvent to enter inside.
　本出願は、２０２１年１０月５日出願の特願２０２１－１６４１５１号に基づく優先権を主張する。当該出願明細書および図面に記載された内容は、すべて本願明細書に援用される。 This application claims priority based on Japanese Patent Application No. 2021-164151 filed on October 5, 2021. All contents described in the specification and drawings are incorporated herein by reference.
　本発明によれば、環境への負荷が少なく、かつ取扱が容易な溶媒に、フッ化ビニリデン重合体が完全に溶解したフッ化ビニリデン重合体溶液が得られる。当該フッ化ビニリデン重合体溶液は、各種分野に使用可能である。 According to the present invention, it is possible to obtain a vinylidene fluoride polymer solution in which the vinylidene fluoride polymer is completely dissolved in a solvent that has a low environmental load and is easy to handle. The vinylidene fluoride polymer solution can be used in various fields.

Claims (6)

  1. 　フッ化ビニリデン重合体と、溶媒とを含むフッ化ビニリデン重合体溶液であり、
    　前記溶媒は分子量１００以上であり、かつエーテル、ケトン、およびエステルから選択される少なくとも１種の構造を有する親和性溶媒を含み、
    　前記フッ化ビニリデン重合体は、以下の（Ａ）～（Ｃ）を満たす、
    　フッ化ビニリデン重合体溶液。
    　（Ａ）フッ化ビニリデン由来の構成単位と、含フッ素アルキルビニル化合物由来の構成単位と、を含有する
    　（Ｂ）ＡＳＴＭ　Ｄ３４１８に準拠した示差熱分析により得られるＤＳＣ曲線の６０℃以上１００℃未満の範囲に、ピークトップを有する
    　（Ｃ）Ｘ線回折測定により得られるＸ線回折パターンにおいて、回折角度が１０°以上１９．９°以下の範囲に少なくとも１つの極大値を有し、回折角度２２．５°以上３０°以下の範囲における最大回折強度が、回折角度１０°以上１９．９°以下の範囲における最大回折強度以下である     A vinylidene fluoride polymer solution containing a vinylidene fluoride polymer and a solvent,
    The solvent contains an affinity solvent having a molecular weight of 100 or more and having at least one structure selected from ethers, ketones, and esters,
    The vinylidene fluoride polymer satisfies the following (A) to (C):
    Vinylidene fluoride polymer solution.
    (A) contains a structural unit derived from vinylidene fluoride and a structural unit derived from a fluorine-containing alkyl vinyl compound; (C) In the X-ray diffraction pattern obtained by X-ray diffraction measurement, the diffraction angle has at least one maximum value in the range of 10° or more and 19.9° or less, and the diffraction angle is 22. The maximum diffraction intensity in the range of 5° or more and 30° or less is less than or equal to the maximum diffraction intensity in the diffraction angle range of 10° or more and 19.9° or less.
  2. 　前記親和性溶媒のオクタノール／水分配係数ＬｏｇＰが０以上である、
    　請求項１に記載のフッ化ビニリデン重合体溶液。     The octanol/water partition coefficient LogP of the affinity solvent is 0 or more,
    The vinylidene fluoride polymer solution according to claim 1.
  3. 　前記溶媒が、イソホロン、ジイソブチルケトン、酢酸アミル、酪酸エチル、酪酸ブチル、プロピオン酸エチルからなる群より選択される少なくとも１種を含む、
    　請求項１または２に記載のフッ化ビニリデン重合体溶液。     The solvent contains at least one selected from the group consisting of isophorone, diisobutyl ketone, amyl acetate, ethyl butyrate, butyl butyrate, and ethyl propionate.
    The vinylidene fluoride polymer solution according to claim 1 or 2.
  4. 　前記含フッ素アルキルビニル化合物が、ヘキサフルオロプロピレンである、
    　請求項１～３のいずれか一項に記載のフッ化ビニリデン重合体溶液。     The fluorine-containing alkyl vinyl compound is hexafluoropropylene,
    The vinylidene fluoride polymer solution according to any one of claims 1 to 3.
  5. 　前記フッ化ビニリデン重合体の濃度が３０質量％以下である、
    　請求項１～４のいずれか一項に記載のフッ化ビニリデン重合体溶液。     The concentration of the vinylidene fluoride polymer is 30% by mass or less,
    The vinylidene fluoride polymer solution according to any one of claims 1-4.
  6. 　ヘーズ値が１８％以下である、
    　請求項１～５のいずれか一項に記載のフッ化ビニリデン重合体溶液。     haze value is 18% or less,
    The vinylidene fluoride polymer solution according to any one of claims 1-5.
PCT/JP2022/036378 2021-10-05 2022-09-29 Vinylidene fluoride polymer solution WO2023058543A1 (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03220272A (en) 1989-11-14 1991-09-27 Japan Synthetic Rubber Co Ltd Organic solvent-based fluororesin coating composition
JP2016025027A (en) * 2014-07-23 2016-02-08 トヨタ自動車株式会社 Method for manufacturing positive electrode for solid battery, method for manufacturing solid battery, and slurry for positive electrode
JP2017160365A (en) * 2016-03-10 2017-09-14 株式会社クレハ Gelatinous electrolyte and preparation method therefor
WO2019230140A1 (en) * 2018-05-31 2019-12-05 株式会社クレハ Polymer solution, method of manufacturing film using same, and resin composition for nonaqueous electrolyte secondary battery
WO2020054548A1 (en) * 2018-09-14 2020-03-19 株式会社クレハ Resin dispersion electrolyte solution, polymer gel electrolyte, production method for polymer gel electrolyte, secondary battery, and production method for secondary battery
WO2021039468A1 (en) * 2019-08-30 2021-03-04 富士フイルム株式会社 Composition containing inorganic solid electrolyte, sheet for all-solid secondary batteries, all-solid secondary battery, method for manufacturing sheet for all-solid secondary batteries, and method for manufacturing all-solid secondary battery
WO2021039950A1 (en) * 2019-08-30 2021-03-04 富士フイルム株式会社 Inorganic solid electrolyte-containing composition, sheet for solid-state secondary batteries, solid-state secondary battery, and methods for producing solid-state secondary battery and sheet for solid-state secondary batteries
WO2021166968A1 (en) * 2020-02-20 2021-08-26 富士フイルム株式会社 Inorganic solid electrolyte-containing composition, sheet for all-solid-state secondary batteries, all-solid-state secondary battery, method for producing sheet for all-solid-state secondary batteries, and method for producing all-solid-state secondary battery
JP2021164151A (en) 2020-03-30 2021-10-11 プレシードジャパン株式会社 Sound collection device

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03220272A (en) 1989-11-14 1991-09-27 Japan Synthetic Rubber Co Ltd Organic solvent-based fluororesin coating composition
JP2016025027A (en) * 2014-07-23 2016-02-08 トヨタ自動車株式会社 Method for manufacturing positive electrode for solid battery, method for manufacturing solid battery, and slurry for positive electrode
JP2017160365A (en) * 2016-03-10 2017-09-14 株式会社クレハ Gelatinous electrolyte and preparation method therefor
WO2019230140A1 (en) * 2018-05-31 2019-12-05 株式会社クレハ Polymer solution, method of manufacturing film using same, and resin composition for nonaqueous electrolyte secondary battery
WO2020054548A1 (en) * 2018-09-14 2020-03-19 株式会社クレハ Resin dispersion electrolyte solution, polymer gel electrolyte, production method for polymer gel electrolyte, secondary battery, and production method for secondary battery
WO2021039468A1 (en) * 2019-08-30 2021-03-04 富士フイルム株式会社 Composition containing inorganic solid electrolyte, sheet for all-solid secondary batteries, all-solid secondary battery, method for manufacturing sheet for all-solid secondary batteries, and method for manufacturing all-solid secondary battery
WO2021039950A1 (en) * 2019-08-30 2021-03-04 富士フイルム株式会社 Inorganic solid electrolyte-containing composition, sheet for solid-state secondary batteries, solid-state secondary battery, and methods for producing solid-state secondary battery and sheet for solid-state secondary batteries
WO2021166968A1 (en) * 2020-02-20 2021-08-26 富士フイルム株式会社 Inorganic solid electrolyte-containing composition, sheet for all-solid-state secondary batteries, all-solid-state secondary battery, method for producing sheet for all-solid-state secondary batteries, and method for producing all-solid-state secondary battery
JP2021164151A (en) 2020-03-30 2021-10-11 プレシードジャパン株式会社 Sound collection device

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